The amounts and compositions of the essential oils in the leaves and fruit of Meyer's lemon in the various vegetation periods have been studied. It has been established that as the fruit ripens the amount of essential oils and of monoterpene hydrocarbons in its peel and in the leaves increases.Institute of Plant Biochemistry, Academy of Sciences of the Georgian SSR. Sukhumi Zonal Experimental Station of Essential-Oil Crops. Sukhumi Experimental Station of Subtropical Crops, All-Union Institute of Plant Growing. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 784–787, November–December, 1985. 相似文献
A new method for the synthesis of dialkyl(ethyl)alanes by the reaction of EtAlCl2 with -olefins in the presence of Mg and a catalytic amount of Cp2TiCl2 (Ti(OPri)4, Ti(OBun)4) in THF was developed. 相似文献
The intramolecular Friedel-Crafts cyclisation of ω-arylalkanoic acids, which is in the benzene series a valuable synthetic route to bicyclic ketones with medium-sized and large rings, has been investigated with ω-(1-naphthyl)alkanoyl chlorides. The lower members, including naphthyl-caproic acid, close the ring at position 2 to form IV. The higher homologous acids show a preference for annellation at 7, making available a new type of heteronuclear naphthalene cyclic ketones (VII). During cyclisation of ω-(1-naphthyl) decanoic acid, the 1,4 ring closure competes with the 1,7 type.
Steric hindrance of resonance as a consequence of “medium ring torsion” was studied in different classes of naphthocyclenones. 相似文献
The crystal and molecular structures of two quarternary salts of 2-oxosparteine (II), the methiodide (IICH+3 • I−) and the methperchlorate (IICH+3 • ClO−4) have been determined on the basis of X-ray and IR data. The studies were performed by analogy to previously investigated quaternary salts of sparteine (I), the methiodide (ICH+3 • I−) and the methperchlorate (ICH+3 • ClO−4). As expected, the configurations and conformations of cationic parts within the two pairs of quaternary salts are identical, except for the structure of their A/B fragments, which in ICH+3 cations have the character of tertiary amines, but in IICH+3 that of lactams.
On the basis of accumulated X-ray and IR data the similarities and differences in the modes of interaction of perchlorate and iodide anions with quaternary cations, and especially with their N+---CH3 groups are discussed. In this discussion are also included the methiodide and methperchlorate of -isosparteine: IIICH+3 • X− (X− = I− or ClO−4) where N+---CH3 groups are cisoidally oriented to the basic nitrogen atoms. The most interesting observations are as follows: (i) When N+---CH3 groups are easily accessible for direct quasi hydrogen bonding interactions with counter anions and when other positive charged groups, for instance lactam groups, are absent in quaternary cations, perchlorate anions interact more strongly than the iodide anions and in consequence introduce conformational changes into the ring with N+---CH3 group as well as into further rings. (ii) Perchlorate and iodide anions interact with N+---CH3 groups similarly and very weakly if at all, when the N+---CH3 groups are for steric reasons inaccessible to counter anions or when in quaternary cations there are additional groups which attract the counter anions electrostatically. The last mechanism operates in both quaternary salts of 2-oxosparteine and this is the reason why their monocrystals are isosteric and IR spectra almost identical. (iii) The sterically hindered N+---CD3 groups in both IIICD+3 • X− salts give rise in their IR spectra to two doubles of sharp, well resolved bands which indicate the presence of two different rotamers stabilized by two modes of weak intramolecular hydrogen bonds with basic N atoms. (iv) In IIICH+3 • X− and IIICD+3 • X− salts the perchlorate and iodide anions do not interact at all with the rotating and vibrating N+---CH3 (N+---CD3) group but the structures of these salts are not isosteric since the perchlorate anions interact more strongly than iodide anions with the A/B fragment of the IIICH+3 cations. This is visible from the shapes and intensities of the so-called “trans” band in the IR spectra of both salts. 相似文献
Raman scattering from Pt(CN)42? adsorbed on Pt colloids (average diameter of 16 A) is compared with the Raman signal from the same amount of Pt(CN)42? in solution. The wavelength dependence of the adsorbate Raman intensity is measured from 308 to 647 nm and compared with a Lorenz/Mie calculation of the enhancement factor for the electromagnetic field intensity on the surface of a Pt sphere as a function of sphere radius and incident wavelength. 相似文献
The rawpH-data, obtained from the potentiometric titrations of the titled ligands with NaOH in 75% (v/v) dioxane-water mixture performed at 20, 30 and 40°C at constant ionic strength (=0.1M-NaClO4), have been adequately corrected for dilution, and solvent effects in order to evaluate thermodynamic dissociation constants. Variance of the latter as a function of temperature has also been accounted for. The differing magnitudes of thermodynamic dissociation constants of the titled ligands have been explained on the basis of the non coplanar orientation of the phenyl ring in the ligands and a comparison has been made with those of unsubstituted benzoylacetone, dibenzoylmethane and acetylacetone.Following similar technique, thermodynamic stepwise and overall formation constants of the titled metal-ligand systems have been obtained and the results correlated with ligand basicity inverse metal crystal radii and second potentials of metals. Decrease in the free enthalpy (–G) of complexation reaction has also been evaluated.
Untersuchung der Gleichgewichte von Mn(II), Mg(II), Ca(II), Sr(II) und Ba(II) mit p-Fluor-, p.-Chlor-, p-Brom-, p-Methyl-benzoylaceton und 1-(4-Fluorphenyl)-1,3-pentanedion
Zusammenfassung Aus der potenitometrischen Titration der Titelverbindungen mit NaOH in 75 (v/v) Dioxan—Wasser bei, 20, 30 und 40°C bei konstanter Ionenstärke (=0,1M-NaClO4) wurden die thermodynamischen Dissoziationskonstanten ermittelt. Verdünnungs-, Lösungsmittel-und Temperatureffekte wurden berücksichtigt. Die unterschiedlichen Dissoziationskonstanten werden mit der Nichtplanarität des Phenylrings in den Liganden erklärt. Außerdem wurden die Komplexbildungskonstanten bestimmt; sie sind in die Diskussion miteinbezogen.
1-Ethyl-2,3-fullerenoaluminacyclopropanes (EtAl)n(2-C60) were synthesized by the reaction of fullerene C60 with an excess of EtAlCl2 in the presence of Mg and using Cp2TiCl2 as the catalyst in a THF--toluene solution at 20 °C. Deuterolysis of fullerenoaluminacyclopropanes afforded a mixture of deuteriofullerenes C60Dm, where m = 6--12. 相似文献
Transmission electron microscopy (TEM) studies on bipyridine (bpy) containing block copolymer systems showed the formation
of nanoscopic polymer–ion complexes through complexation with copper(I) ions which segregated to highly ordered columnar domains
of mesoscopic dimensions. The domains, i.e. stacks of [(bpy)2Cu(I)] complex moieties could be visualized by complementary TEM techniques. First, electron energy loss spectra (EELS) showed
the absorption edges of copper and nitrogen, which are specific for the bipyridine copper complexes. The element spectroscopic
imaging (ESI) technique allowed the imaging of the net copper and net nitrogen distribution, and the coinciding pictures exhibited
a microphase separated system in the case of a 3-block copolymer with complexed end segments. High resolution elastic bright
field images showed interference lines with a line to line distance of about 8 A which could be related to the Cu–Cu distance
in staggered Cu(I)–bipyridine complexes.
Received: 6 August 1997 Accepted: 28 April 1998 相似文献