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1.
The structures of two new cycloartane triterpenoids, cycloalpigenin A and cycloalpioside A, isolated from Astragalus alopecurus Pall. (Leguminosae) have been established on the basis of chemical transformations together with1H,13C, and 2D1H-1H and1H-13C chemical shift correlation NMR spectroscopy and IR, mass, and CD spectra. Cycloalpigenin A is 3,16,25-trihydroxy-20R,24S-epoxycycloartan-12-one, and cycloalpioside A is cycloalpigenin A 3-O--D-xylopyranoside.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, FAX (3712) 62 73 48. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 379–385, May–June, 1994.  相似文献   

2.
-Picolinium-p-chlorophenacylide (-PCFY) acts as a retarder for polymerization of N-vinyl pyrrolidone. The polymerization runs were carried out at 60°C using benzene as an inert solvent. The kinetic equation for the present system may be written asR p [-PCPY]–1.0 [AIBN]0.66[N-VP]1.0. The value of overall energy of activation for polymerization in presence and absence of-PCPY was computed as 44.0 and 42.3 kJ mol–1, respectively. The inverse relationship ofR p and¯M v with-PCPY suggests that-PCPY acts as a polymerization retarder. The retarding effect is also evidenced by higher initiator exponent value and higher value of energy of activation in presence of ylide. A mechanism is also proposed in which polymer propagating chain combines with one ylide component to give resonance stabilized radical.  相似文献   

3.
2,3-Dihydroxypyridine loaded (via –N=N–linker) Amberlite XAD-2 (AXAD-2-DHP) was prepared and characterized by elemental analyses, TGA and FT-IR spectra. It (1g packed in a column of 1cm diameter; surface area 135.5m2g–1) was found to be an effective solid phase sorbent for enriching Zn2+, Mn2+, Ni2+, Pb2+, Cd2+, Cu2+, Fe3+ and Co2+ at pH 3.5 to 7.0 using flow rates between 1.0–5.0mLmin–1. For desorption (recovery 97.0–99.8%) of the metal ions, 8 to 10mL of 2.0molL–1 HCl or 1.5molL–1 HNO3 at a flow rate of between 2.0 and 4.0mLmin–1 were found most suitable. The t1/2 (time for 50% sorption) is between 2 and 10min when a 50mL solution (containing a total amount of metal of 2mg) was equilibrated with 0.5g of resin. Sorption of all metal ions except Pb2+ follows the Langmuir model, whereas for Pb the data fits with the Freundlich model. The sorption capacity is between 60.7 (for Cd) and 406.7 (for Cu) µmolg–1. The resin can withstand an acid concentration of 6molL–1 and can be reused for thirty cycles of sorption–desorption. The preconcentration factor varies between 100 and 300. For Cd, Ni and Cu the sorption capacity of 2,3-dihydroxypyridine loaded cellulose is lower than that of the present resin. The tolerance limits of electrolytes, humic acid, complexing agents, Ca2+ and Mg2+ in the enrichment of all metal ions are reported. The limits of detection are 3.88, 5.37, 8.72, 13.88, 4.71, 1.24, 0.59 and 0.30µgL–1 for Zn2+, Mn2+, Ni2+, Pb2+, Cd2+, Cu2+, Fe3+ and Co2+, respectively. The calibration curves for flame AAS determination were linear in the ranges 0.018–1.0, 0.067–5.0, 0.2–5.0, 0.9–20, 0.028–2.0, 0.077–5.0, 0.19–10 and 0.1–3.5µgmL–1, respectively. All the eight metal ions in river and synthetic water samples, Co in vitamin tablets and Zn in milk samples have been quantitatively enriched with Amberlite XAD-2-DHP and determined by flame atomic absorption spectrometry.  相似文献   

4.
It is shown that substituting activities of individual ions for their concentrations in the equation for the ionic strength of solution substantially extends application of the first approximation of the Debye–Hückel theory for electrolytes of different valence. The obtained relationship predicts a changeover from the square root law in the charge region where the average distance between ions lis smaller than the ionic-atmosphere thickness 1/, to the cube root law, at l> 1/. The increasing deviation from experimental data upon going from LaCl3solutions to La2(SO4)3is attributed to the formation of ionic pairs LaSO4 +.  相似文献   

5.
The ytterbium phenylethynyl compound (PhCC)2Yb(THF)4 reacts with trimethylsilicon, triphenylgermanium, and triphenyltin chloride in tetrahydrofuran (THF) at room temperature to give the corresponding cross-coupling products: phenylethynylytterbium chloride PhCCYbCl(THF)2 and ytterbium chloride YbCl2(THF)2.  相似文献   

6.
MCD, electronic absorption, external heavy atom, and crystal field data are presented for the low energy region (2 E g, 2 T 1g, 4 T 2g) and high energy region (2 T 2g, 4 T 1g) of Cr(dtp)3, Cr(dtc)3, and Cr(exan)3. At low energy, MCD intensities of 2 E(2 E g) and 2 E(2 T g) are as large or larger than 4 T 2g, and the MCD technique is advantageous over electronic absorption in this respect. The MCD positions of 2 E g and 2 T 1g are nearly the same for these molecules ( 13 kK and 13.6 kK) · 4 T 2g of this region appears trigonally split ( 500 cm–1) in the MCD of dtp but to a smaller extent than in the electronic crystal spectrum of Lebedda and Palmer ( 600 cm–1). MCD did not resolve such components for exan and dtc. The higher energy region includes 2 T 2g and 4 T 1g, and the combined MCD and electronic absorption data of the three compounds taken together lead us to conclude the ordering 2 A 1(2 T 2g)<2 E(2 T 2g)<4 E(4 T 1g). The potentially useful external heavy atom affect on the solution-observed electronic 2 E and 4 E bands of Cr(dtp)3 did not shed additional light on this order of E states. Finally, it is concluded that the order of 4 T 1g and 2 T 2g cannot be decided from O h crystal field calculations because of experimental uncertainties about choosing centers of gravity. In addition, 4 T 1g and 2 T 2g are close together so that ordering 2 E<4 E does not guarantee 2 T 2g<4 T 1g. However, it can be concluded that the ratio C/B4 is not correct, whereas the larger 7<(C/B)<8 is consistent with the data of all three molecules because of small B parameters ( 0.4). Locating OO transitions may somewhat decrease C/B and Dq.
Zusammenfassung In der vorliegenden Arbeit werden folgende Meßergebnisse mitgeteilt; MCD, elektronische Absorption, Einfluß eines äußeren schweren Atoms sowie Kristallfelddaten für den Bereich niedriger Energie (2 E g, 2 T 1g, 4 T 2g) und den Bereich hoher Energie (2 T 2g, 4 T 1g) von Cr(dtp)3, Cr(dtc)3 und Cr(exan). Bei niedriger Energie sind die MCD-Intensitäten von 2 E(2 E g) und 2 E(2 T 1g) genau so groß, oder größer als 4 T 2g, und die MCD-Technik bietet Vorteile gegenüber der elektronischen Absorptionsmethode. Die MCD-Werte von 2 E g und 2 T 1g sind für die genannten Moleküle etwa gleich ( 13 kK und 13,6 kK). 4 T 2g dieses Gebietes erscheint trigonal aufgespalten ( 500 cm–1) bei MCD von dtp, aber in einem geringeren Maß als im elektronischen Kristallspektrum von Lebedda und Palmer ( 600 cm–1) MCD löste solche Komponenten bei exan und dtc nicht auf. Der Bereich höherer Energie enthält 2 T 2g und 4 T 1g, und aus der Kombination von Daten der MCD-Methode sowie der elektronischen Absorption schlossen wir auf die Anordnung 2 A 1g(2 T 2g)<2 E(2 T 2g)<4 E(4 T 1g). Der möglicherweise nützliche Effekt eines äußeren schweren Atoms auf die in Lösung beobachteten elektronischen 2 E- und 4E-Banden von Cr(dtp)3 brachte bezüglich dieser Anordnung der E-Zustände nichts Neues. Weiterhin wird gefolgert, daß die Ordnung von 4 T 1g und 2 T 2g nicht aus O h-Kristallfeldberechnungen entschieden werden kann, da experimentelle Unsicherheiten bezüglich der Wahl von Schwerpunkten bestehen. Außerdem liegen 4 T 1g und 2 T 2g nahe zusammen, sodaß aus der Anordnung 2 E<4 E nicht notwendig 2 T 2g<4 T 1g folgt. Es kann jedoch gefolgert werden, daß das Verhältnis C/B4 nicht korrekt ist, während 7<(C/B)<8 konsistent mit den Daten aller drei Moleküle ist, da die B-parameter klein sind (0,4). Die Vokalisierung der OO-Übergänge könnten C/B und Dq etwas erniedrigen.


Presented in part at the 161st American Chemical Society National Meeting, Los Angeles, California, March–April, 1971.

NDEA Pre-Doctoral Fellow.  相似文献   

7.
Studies by 1H NMR spectroscopy and X-ray diffraction analysis revealed hindered rotation of the aromatic substituent about the CAr—N bond in ortho-substituted (except for o-fluorine-substituted) phosphorus-containing carbamates. The energy barriers to rotation (G c ) and coalescence temperatures (T c) determined by the coalescence method increase with increasing volume of the ortho substituent. Conformations resulting from rotation of the ortho-substituted aryl group about the CAr—N bond were analyzed by quantum-chemical methods, potential curves were constructed, and differences between the conformational energies and the heights of rotation barriers were estimated. The theoretical rotation barriers change in parallel with the experimental values of G c ; however, the theoretical values are much smaller in magnitude.  相似文献   

8.
The structural characterizations of some copper(I) halide (CuX) adducts with norbornadiene (nbd) are recorded. CuCl : nbd (1:1)4 (a redetermination), (2:1)2(|), are systems both based around Cu4Cl4 cubane-type cluster arrays. CuBr : nbd (7:3)(|)( 0.5 MeOH), a complex polymer with 3-symmetry, is believed to be the complex previously described as an adduct of 2:1 stoichiometry. Attempts to obtain an iodide counterpart have resulted in the definition of an ephemeral adduct CuI : MeCN (3:2)(|). 0.5 C7H8 in which, remarkably, the nbd is uncoordinated; the complex is a polymer, related to the [AgX(quinoline)](|) (X = Cl, Br) saddle polymer.  相似文献   

9.
Triterpene glycosides from Pulsatilla chinensis   总被引:1,自引:0,他引:1  
Four triterpene glycosides were isolated from the roots of Pulsatilla chinensis (Bunge) Regel (Ranunculaceae). Two new glycosides, chinensiosides A (1a) and B (2), were identified as 3-O-[-L-rhamnopyranosyl-(12)--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid and 3-O-{-L-rhamnopyranosyl-(12)-[-D-glucopyranosyl-(14)]--L-arabinopyranosyl}-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid. The other two glycosides were identified as previously known hederasaponin C (3) from Hedera helix and glycoside III (4) from Pulsatilla cernua.  相似文献   

10.
The encapsulation of the acid/base conjugated system salicylic acid(HSA)/salicylate (SA-) by hydroxypropyl--cyclodextrin (HPBCD) has beenstudied through fluorescence emission enhancement measurements in aqueoussolutions at 25 °C. With the aim of analyzing the crucial importance ofa proper and cautious choice of the pH of the medium (i.e. choice of thebuffer), the study has been carried out at pH = 1, 2, 4 and 7. Since the pKa of the HSA/SA- system is 2.95 at 25 °C, the presence of the protonated(HSA) and non-protonated (SA-) forms suitable for inclusion by cyclodextrinvary appreciably within the different pH conditions: 99% HSA,1% SA- at pH = 1, 90% HSA, 10% SA- at pH = 2,10% HSA, 90% SA- at pH = 4, and 0% HSA,100% SA- at pH =7. The association constants K CD : HSA and K CD: SA- have been determined in all cases by using a nonlinear regressionanalysis of the experimental data at three different em. The effectof the pH of the medium on all the equilibria involved as well as in the Kvalues is fully discussed. The 8-anilino-1-naphthalene sulfonate (ANS) +-cyclodextrin (-CD) system, widely reported in literature, hasinitially been studied to check the experimental protocol and the numericalmethod.  相似文献   

11.
The title compound, [cis-Co(en)2(NO2)2](NO2) (1), crystallizes in the polar, nonenantiomorphic, monoclinic space group, Cc, with lattice constants:a=9.198(2) Å,b=12.444(2),c=9.963(3), and=96.76(2)°;V=1132.39 Å3 andd(calc;Z=4) =1.860 g cm–3. Thus, with NO2– as the counteranion, [cis-Co(en)2(NO2)2] crystallizes in a heterochiral lattice containing racemic pairs of cations. A total of 2699 data were collected over the range of 4°270°; of these, 1859 (independent and withI3(I)) were used in the structural analysis. Data were corrected for absorption (=15.465 cm–1) and the relative transmission coefficients ranged from 0.9934 to 0.7112. Refinement was carried out for both lattice polarities and the finalR(F) andR w (F) residuals were, respectively, 0.0242 and 0.0202 for (–––) and 0.0264 and 0.0243 for (+++). Thus, the former was selected as correct for our specimen.Unlike all previous X-ray diffraction studies of the structural properties of the cation [cis-Co(en)2(NO2)2]+, which are found to have a pair of oppositely configured en rings [i.e., () or ()], we find that in1 the cations are in the lowest energy conformation and configuration; i.e., () or (). We attribute this change in configuration to the formation of strong interionic hydrogen bonds between nitrite anion oxygens and the axial—NH2 hydrogens, which markedly weaken the intermolecular and intramolecular hydrogen bonds between ligand—NO2 oxygens and the hydrogens of those same amine moieties. Thus, the nitrite anions behave exactly as nitrate anions, except that the hydrogen bonds found here are stronger than those formed by the latter. This is as expected since the negative charge is delocalized over two, instead of three, oxygens.  相似文献   

12.
The diacetylenic adducts, Fe2(CO)6{-EC(H) = C(C CMe)E} (E = E, E E; E, E = S, Se, Te) (1–8) have been obtained from the room temperature stirring of Fe2(CO)6(-EE) with HC CC CMe in methanol solvent containing sodium acetate. Compounds 1–8 have been characterized by IR and multinuclear NMR (1H, 13C, 77Se, and l25Te) spectroscopy. Trends in the chemical shifts of 77Se and 125Te NMR spectra of Fe2(CO)6{-EC(H) = C(C CMe)E} with a variation of EE are discussed.  相似文献   

13.
Summary The syntheses of the ethyltetramethylcyclopentadienyl complexes Ru(5-C5Me4Et)(CO)2Cl, CO( 5-C5Me4Et)(CO)2, and [M( 5-C5Me4Et)Cl2]2 (M = Rh or Ir) are described; the ruthenium complex reacts with triphenylarsine to give Ru( 5-C5Me4Et)(AsPh3)(CO)Cl.1H and13C n.m.r. spectra, i.r. spectra and the physical properties of the compounds are discussed and contrasted with the known C5H5 and C5Me5 analogues.  相似文献   

14.
The rate constants for Br(2P1/2) and Br(2P3/2) atoms in the reaction Br+CH3FHBr+CH2F in photobromination of CH3F have been determined. Their ratio is 10–(2.6±0.5) exp(10100±1000/RT) in the temperature range of 60–200 °C.
Br(2P1/2) Br(2P3/2) Br+CH3FHBr+CH2F CH3F. 60–200 °C 10–(2,6±0,5) exp (10100±1000/RT).
  相似文献   

15.
The reaction of the heterobinuclear metal -allenyl complexes (PPh3)2Pt(- 1: 2 , -C(R)=C=CH2)Ru(CO)Cp (R=H (1), Ph (2)) with (PPh3)AuO3SCF3 in THF at –78°C to room temperature affords the trimetallic products [(PPh3)2Pt( 2-CO)RuCpAu(PPh3)( 3- 1: 3: 1-CH2CCR)]+O3SCF 3 (R=H (3), Ph (4)) in 46 and 55% isolated yield, respectively. The products were characterized by a combination of elemental analysis, FAB mass spectrometry, and IR and 1H, 13C, and 31P NMR spectroscopy. The structure of 4 was elucidated by a single-crystal X-ray analysis. The crystal contains discrete trimetallic RuPtAu cations and CF3SO 3 anions. In the cation, a Pt–Ru bond of 2.7171(6) Å is supported by a semibridging CO and a CH2CCPh allyl, which is 3-bonded to Ru, and 1-bonded to each of Pt (through the CPh carbon) and Au (through the central carbon). The Ph3P–Au–C fragment is close to linear (175.0(2)°), and the coordination environment around Pt is distorted square planar. Complex 3 appears to have the same type of structure as 4 from spectroscopic data.  相似文献   

16.
Summary New chiral cyclopentadienyl-titanium and-zirconium complexes Cp2TiCl2, CpCpTiCl2 and Cp2ZrCl2 (Cp=5 -cyclopentadienyl and Cp=substituted cyclopentadienyl), have been synthesized. The (S,S)-3 complex, which forms red plate crystals, has been studied by x-ray analysis. It belongs to the monoclinic space groupC2, witha 23.963(3),b 6.6470(6),c 12.6618(9) Å, 103.089(7)°, V=1964.4(3) Å3 and Z=4. The structure was relined to an R factor of 0.048 for 868 observed reflections.  相似文献   

17.
New cationic complexes [(6-C13H10)Fe(5-Cp*)]PF6 and [(6-9-CH3-C13H9)Fe(5-Cp*)]PF6 were obtained by the reaction of Cp*Fe(CO)2Br with fluorene and 9-methylfluorene, respectively. Deprotonation of these complexes byt-BuOK in THF affords zwitter-ionic compounds (6-C13H9)Fe(5-Cp*) and (6-9-CH3-C13H8)Fe(5-Cp*) (A). WhenA is heated in nonane at 150 °C it undergoes 65 inter-ring rearrangement with the formation of hexamethyldibenzoferrocene (B). The electrochemical behavior ofA andB was studied by cyclic voltammetry. One-electron reduction ofA andB to the corresponding radical anions induces inter-ring haptotropic rearrangementA .–B .–. The equilibrium in the 19 state is shifted to the 6-isomeric radical anionA .–, while in the 18 precursors, it shifts to the 5-isomerB.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 319–324, February, 1994.The authors are grateful to D. V. Zagorevskii (A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences) for recording and interpreting the mass spectra, and to A. A. Borisenko (Moscow State University) for recording the NMR spectra.This work was financially supported by the Russian Foundation for Basic Research (Grant 93-03-5209).  相似文献   

18.
Muonium (Mu=++e-) is the bound state of a positive muon and an electron. Since the positive muon has a mass about 1/9 of the proton, Mu can be regarded as an ultra light isotope of hydrogen with unusually large mass ratios (MuHDT=1/9123). The muon spin rotation technique (SR) relies on the facts that (1) the muon produced in pion decay, + + + , is 100% spin polarized and (2) the positron from muon decay is emitted preferentially along the instantaneous muon spin direction at the time of the muon decay.In transverse field SR (TF-SR), the precession of the muon spin in muonium substituted radicals is directly observed by detecting decay positrons time differentially. From observed radical frequencies, the hyperfine coupling constants (A ) of C2H4Mu, C2D4Mu,13C2H4Mu, C2F4Mu, and C2H3FMu are determined. In the longitudinal field avoided level crossing (LF-ALC) technique, one observes the resonant loss of the muon spin polarization caused by the crossing of hyperfine levels at particular magnetic fields. The LF-ALC method together with the information onA obtained from TF-SR allows one to determine the magnitude and sign of the nuclear hyperfine constants at - and -positions. Results are compared with hydrogen substituted ethyl-radicals and isotope effects are discussed.  相似文献   

19.
The thermodynamic parameters for the interaction of Cu2+, Ni2+, Co2+, Cd2+, andAg+ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag+ exhibited remarkably higher complexation selectivity.Ag+ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg+–M2+ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag+ was observed in both single and competitiveAg+–M2+ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P2N2) with silver,[Ag(P2N2)] (NO3), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P21/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) 3 and Z = 4.  相似文献   

20.
The thermal reactions of Ru3(CO)12 with RCOCH=CHPh (R=Me, p-MeC6H4) in hydrocarbon solvents lead to the formation of a series of complexes, several of which have been isolated as individual compounds by chromatography. The dinuclear complex Ru2(-H)(CO)6(-MeCOCH=CPh) and the tetranuclear complex Ru4(-H)(-CO)(CO)7(p-MeC 6H4 COCH=CPh)(-p-MeC6H4COCH=CPh)(4-p-MeC6H3COCH=CHPh) are characterized by an X-ray structural study. The structures of other reaction products are discussed on the basis of spectral data. The reactions are accompanied by reduction of the starting enones to the corresponding unsaturated ketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1285–1293, July, 1993.  相似文献   

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