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1.
13Cmr spectra show complete absence of scrambling of an 18O label in recovered after partial conversion to thereby precluding an -methylation mechanism for the bimolecular formation of from . 相似文献
2.
Structure of deacetylazadirachtinol application of 2D1H-1H and 1H-13C shift correlation spectroscopy
Isao Kubo Takeshi Matsumoto Akiko Matsumoto James N. Shoolery 《Tetrahedron letters》1984,25(42):4729-4732
A new insect antifeedant, and ecdysis inhibitor deacetylazadirachtinol, was isolated from (Meliaceae) collected in Haiti and its structure (1) was elucidated by the spectral comparison with azadirachtin using two-dimensional 1H-1H and 1H-13C shift correlation spectroscopies. 相似文献
3.
A C25 alkane (1) proposed previously to occur in and 1 and to be a sedimentary biological marker for methanogenic bacteria9, has been synthesised and its occurrence confirmed. 相似文献
4.
Thomas J. Simpson 《Tetrahedron letters》1981,22(38):3785-3788
Incorporations of [1-13C]?, [2-13C]?, [1,2-13C2]-acetates and [13C]-methionine into anditomin, a metabolite of , indicate its formation by a mixed polyketide-terpenoid biosynthetic pathway similar to that elucidated for andibenin; observations are made on the possible biosynthetic relationship of the metabolites with austin and terretonin, mycotoxins recently isolated from and respectively. 相似文献
5.
The nebulizing process in inductively-coupled plasma emission spectrometry is a major source of the instrumental variability; an attempt has been made to isolate this source so that its influence on the final result could be evaluated. Direct measurements of the time-dependent variations of the sample supply to the plasma were achieved by using a device based on the light-scattering property of nebulized test solutions. The noise from the nebulizer and of the emission signal was characterized by autocovariance functions and power spectral densities. The types of noise observed showed f- and f- character, depending on the concentration of the test elements employed. Cross-covariance revealed a strong correlation between the noise sources considered. The applicability and limitations of possible correction and electronic filtering procedures are indicated. 相似文献
6.
The synthesis of [O9,24] [2.1.2.1]metacyclophane-9-ene and of its dehydrogenation products^the new pyrenocyclophanes , , , and , is described; their structures are discussed in connection with their 1H-NMR-spectra. 相似文献
7.
Jan A. Glinski Balawant S. Joshi Szu-yinq Chen S.William Pelletier 《Tetrahedron letters》1984,25(12):1211-1214
A novel C19-diterpenoid alkaloid designated as tatsinine has been isolated from the roots of and its structure (3) has been derived from 1H NMR and 13C NMR spectroscopic evidence. 相似文献
8.
The synthesis of tetracyclo[5.4.1.04,12.09.12]dodecan-6-one via an intramolelecular photocycloaddition, its reduction to the hydrocarbon and its ring-contraction to tetracyclo-[4.4.1.03,11.09,11]undecane derivative is described. 相似文献
9.
The chiral axis in the title glycine derivative has allowed its resolution into enantiomers: the barrier Δ G≠ for racemisation (rotation around the bond) is 26.2 Kcal mol?1. 相似文献
10.
The 13C-NMR spectra of the alkaloid ajmaline () and its stereoisomers isoajmaline (), sandwichine () and isosandwichine () are reported. The different stereochemistry at C (17), C(20) and C(21) of the four isomers can be directly ascertained by chemical shifts data. 相似文献
11.
Optical absorption and emission spectra are reported for single crystals of the cubic elpasolite Cs2NaSmCl6. The variable temperature spectra obtained at high resolution are assigned using energies and relative intensities. Transitions from the ground level, 6H to cystal fi levels of 6H-, 6F-, 4G-, 4F,, 4I, and 6P, are located and characterized. Intensity calculations are reported for magnetic dipole allowed transitions. The dominance of vibronic intensity in 6H→6F - and 6P, transitions is accounted for qualitatively through the ligand polarization model involving quadrupole metal (Sm3+)-ligand (Cl?) interaction mechanisms. The Eu″(6H)→E′(6H) Eu′(6F) no-phonon transition is postulated to be pure electric quadrupole allowed. The ground state magnetic moment is determined to be very small from magnetic circular dichroism (MCD) spectra.This study has led to the assignment of nearly all of the crystal field levels in the visible and IR region for Cs2NaSmCl6. A total of 27 such levels were identified, 17 from no-phonon transitions and the rest from vibronic transitions. The magnetic dipole intensity calculated using intermediate coupling Oh wavefunctions along with a crystal field analysis of the splitting pattern was used in the assignment of the levels. Vibronic bands were observed for all transitions and their vibrational symmetries were tentatively assigned. MCD data were used to determine the magnet moment of the ground state. 相似文献
12.
The photolysis of phenyl alkyl ketones adsorbed on a number of commonly available zeolites (molecular sieves) can result in dramatic changes in Type I/Type II photochemistry.The photochemistry of ketones in ordered environments is a topic of current interest2–4. Environmental effects can have important influence on the conformational flexibility of organic molecules, which in turn can affect the outcome of photochemical reactions5. Two recent reports2,3 on the Norrish Type II reaction in ordered media prompts us to report our initial studies of the photochemistry of a number of phenyl alkyl ketones adsorbed in zeolites.Zeolites are crystalline aluminosilicates of usually well-defined structure6. Within the zeolite framework are a system channels and cavities of varying dimensions(2 – 13Å)6, some of which are capable of adsorption of large organic molecules (e.g., substituted benzenes). Thus the possibility that the internal spaces (or void volumes) of zeolites can exert topological control on organic photochemical reactions warrants investigation, since it is well-known that zeolites display shape-selective catalytic and adsorptive properties in important industrial chemical processes10. However, only a handful of reports of photochemical reactions on zeolites are known4,7–9; the majority of these concern the catalytic splitting of water9. In this study, several commonly available zeolites were studied, and the results are compared to those obtained in homogeneous solution.Phenyl alkyl ketones - were employed in this study. The photochemistry of valerophenone , octanophenone , and α,α-dimethylvalerophenone is relatively well-understood in solution11–13. For and , the photobehaviour is characterized by Type II reaction, to give a triplet 1,4-biradical, which can either fragment, to give acetophenone, or cyclize, to give and cyclobutanols (eqn.1). Type I reaction in not observed. In solution, the ratio of fragmentation of cyclization (F/C) products is ~ 4 for and . In general, the isomer dominates, with t/c = 3 – 5 in benzene, and decreasing to a limit of 1 in more polar solvents (MeOH or micelles)11-–13. For . Type I reaction is observed in addition to Type II. The ratio of Type I/Type II product has been reported to be 0.3 in benzene without added thiol, and 0.6 with added thiol11.Ketones and were deposited on Zeolites Na+-A, Na+-X, Na+-Y, Na+-Mordenite and resembling is also possible, from which cyclization is prohibited. For , Type I reaction is known to compete with the Type II process11. Adsorption of this ketone on Silicalite results in reaction via the least-motion pathway, namely Type I reaction, to give benzaldehyde as the aromatic product. Thus the behaviour of this ketone on Silicalite is quite consistent with the explanation offered for and .Na+-Y is a large pore zeolite, with a pore diameter of ~8 Å and an internal cavity (supercage) of ~13 Å6. Additionally, we have found from related studies16 that of the zeolites capable of adsorbing benzene-type molecules studied in this work, Na+-Y allows the greatest degree of molecular mobility for photogenerated benzyl radical. Thus the observed F/C ratios of less than unity for this zeolite probably reflects the increased mobility of the photogenerated 1,4-biradical, allowing it to undergo ring closure readily. Interestingly, this zeolite also gave an t/c ratio for cyclobutanols of .The results for the other zeolites are not readily distinguishable from those observed in solution, although two of these (Na+-X and Na+-Mordenite) are capable of adsorbing - 6. In any event, these two zeolites offer a medium for Type I/Type II reaction which essentially duplicate the behaviour in solution without the presence of solvent. Additional studies are in progress to further study the use of zeolites as a medium for photochemical reactions. 相似文献
13.
Dialkylcarbodiimides, , react with iminium salts, , to afford the formal 1,1-diaminosubstituted 2-azaallenium salts . According to dynamic NMR measurements compounds must be regarded as alkylidene-guanidinium salts , undergoing a fast topomerization via a transition state with allene geometry (2G=265 = 45.9 ± 1 kJmol-1 for ) and a slower rotation around the peripheral C-N bonds (transition state ; 2G=290= 58.0 ± 1 kJmol-1 for ). 相似文献
14.
1-Methyl-2-(1′-cyano-1′-trimethylsilyloxy)alkyl-1H-imidazoles () were easily prepared from the corresponding stable carbonyl compounds, 1-methyl-2-acyl- 1H-imidazoles (). When the quarternary salts of were treated with various nucleophiles, reactive acyl species, which was presumed to be acylcyanide (), was generated in situ under CC bond fission to result in producing the corresponding acylated compounds (–) in good yields. 相似文献
15.
J.L. Breton F. Camps J. Coll L. Eguren J.A. Gavin A.G. Gonzalez X. Martorell C. Miravitlles E. Molins J. Torramilans 《Tetrahedron》1985,41(15):3141-3146
A new heliangolide has been isolated from aerial parts of , and identified as (6,10)(3,3a,4,lla)-3a,5,8,11a--tetrahydro-4-acetoxy-3,6, 1O-trimethyl-2,9 (3, 4) -cyclodeca[b] furandione. The structural elucidation of the new compound, named heliangolidin, was carried out by spectral means (MS, IR, 1H and 13C NMR, and two dimensional 1H-13C chemical shift correlations) and X-ray diffraction analysis. 相似文献
16.
The geometries and the 1H chemical shifts of dihydropyrene and its benzannelated derivatives – have been studied by means of semiempirical quantum chemical procedures. The calculated bond lengths of and proton shifts of – are in good accord with the corresponding experimental values. We show that monobenzannelation in – causes considerable bond length alternation in the [14] perimeter and hence reduced diatropocity. The same is true for the phenanth-fused dibenzannelated compounds and . On the other hand we report evidence that anth-fused dibenzannelated dihydropyrenes , , and should be characterized by symmetric geometrical structures without significant bond length alternation thus leading to enhanced diatropicity. 相似文献
17.
A new synthesis of (±), (+)- and (-)-lineatin (3,3,7-trimethyl-2, 9-dioxatricyclo [3.3.1.04,7] nonane, ) was achieved. The stereochemistry of (+)-lineatin was established as 1, 4, 5, 7 by an X-ray crystallographic analysis of an intermediate . 相似文献
18.
Ronald D. Brown Peter D. Godfrey Donald C. McGilvery Jonathan G. Crofts 《Chemical physics letters》1981,84(3):437-439
Microwave—optical double resonance signals have been detected in a mass-selected ion-beam spectrometer for 12C16O+. With the optical excitation of fluorescence from the R1 () line of the (0,0) band of the A2Π ← X2∑ transition of 20350.6 cm?1, the microwave resonances occurred at 118101.8 ± 0.2 MHz and at 117694 ± 2 MHz corresponding to the N= 1, J = ← N = 0, J = and the N = 1, J = ← N = 0, J = transitions. 相似文献
19.
W.David Ollis Julia Stephanidou Stephanatou J.Fraser Stoddart Gulten G. Unal David J. Williams 《Tetrahedron letters》1981,22(23):2225-2228
An X-ray structure analysis shows that the 5, 18-dimethyl derivative () of the title compound () crystallises from xylene as a 1:1 inclusion compound in which the host molecules adopt propeller-like conformations ( and *) with almost perfect 2 symmetry. Dynamic 1H n.m.r. spectroscopy shows that the 5, 18-dibenzyl derivative () of () forms a 1:1 inclusion compound with ethanol in the solid state and undergoes ring inversion ( ? *) between enantiomeric propeller-like conformations in solution against a barrier of 21.1 kcal mol?1 相似文献
20.
The half-wave reduction potentials, E's, of ten acetophenone derivatives have been determined in acetonitrile. A linear free-energy relationship was obtained between E and the n,π* triplet energy. This correlation enabled an estimate to be made of the n,π* triplet energy of those acetophenones with π,π* lowest triplet. 相似文献