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21.
Gyrgy Frter 《Helvetica chimica acta》1975,58(2):442-447
Through sequential Claisen- and Cope rearrangements the chainlengthening of allylic alcohols by one isoprene unit was achieved. Treatment of (E)-1a first with lithium N-cyclohexyl-N-isopropylamide at ?70°, followed by trimethylsilylchloride and warming up to room temperature yielded after work-up 3a (R = H), which rearranged at 156° in high yield to (E/Z)-4a. An analogous reaction sequence transformed 6 to 8. Choosing lithium N-methylanilide as a base (E/Z)-9 was selectively rearranged to 12, which was converted to the Cecropia juvenile hormone precursor (E/Z)-4b. 相似文献
22.
Mátyás Milen László Hazai Pál Kolonits György Kalaus Lajos Szabó Ágnes Gömöry Csaba Szántay 《Central European Journal of Chemistry》2005,3(1):118-136
Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected.
Dedicated to Professor Károly Lempert on his 80th birthday. 相似文献
23.
Schultz György Hargittai István Rot Nicolette Bickelhaupt Friedrich 《Structural chemistry》1998,9(3):209-214
The molecular structure of 1,3,5-tris (trimethylstannyl) benzene has been determined by gas-phase electron diffraction. The C — C bond length is in good agreement with that in benzene. In agreement with the somewhat electron-releasing character of the substituents, the endocyclic bond angles at the substituents are somewhat smaller than 120°. The mean value of Sn — C bond lengths is greater than that in tetraphenyltin and tetramethyltin. The SnMe3 groups appear freely rotating around the Caryl — Sn bonds. The following bond lengths (r
g) and bond angles were determined: (Sn — C)mean 2.150 ± 0.007 Å, C — C 1.399 ± 0.005 Å, (C — H)mean 1.105 ± 0.006 Å, < C — C(Sn) — C 117.7 ± 1.7º, < Caryl — Sn — Cmethyl 106.7 ± 0.7º < Sn — C — H 111.5 ± 0.9º. 相似文献
24.
The Cyclopropa[c]chromenes 14 , trans-and cis- 15 , trans-and cis- 16 and 17 rearrange on heating > 200° in N, N-diethylaniline to give 2-alkyl-2H-chromenes 7, 8, 21, 22. The rate determining step of this rearrangement is the ‘homoelectrocyclic’ ring opening of the cyclopro-pa[c]chromenes to give ω-allyl-quinomethanes of type 4. These intermediates show fast [1,5s] and [1,7a] H-shifts, followed by electrocyclic ring closure. Deuterium labelling experiments are in agreement with this mechanism. The remarkable dependence of the rates of rearrangement with respect to the stereochemistry of the cyclopropa[c]chromenes (cf. table 2) suggests that in the first step only one of the two possible disrotatory modes of ring opening is involved. 相似文献
25.
The reaction takes place on Cd-containing Lewis sites, whereas the irreversible adsorption and condensation of product acetaldehyde on acidic OH groups of Cd-X, FAU catalyst results in deactivation. Preadsorbed ammonia moderates the deactivation, because it reacts with acetylene, and pyridine homologues are formed which block the accessible OH groups. Since in divalent cationic forms of clinoptilolite no OH groups are generated, Cd-clinoptilolite proved to be a catalyst of permanent activity.
, Cd, — OH FAU, Cd-X. , .. , OH . OH, Cd- .相似文献
26.
Summary The lipophilicity of 28 modified crown ether derivatives was determined by reversed-phase thin-layer chromatography (RPTLC) using various organic phases and supports. The lipophilicity values determined in different RPTLC systems showed good correlations, however the quality of the organic phase (methanol, acetone, acetonitrile) and the support characteristics influenced to a small extent the determination. 相似文献
27.
Summary A new, highly sensitive and selective gas chromatography method, using radiochemical detection (GC-DR) was developed for the
selective determination of3H-labelled deramciclane and its N-desmethyl metabolite in dog plasma. Inter-day accuracy and precision, as well as system
suitability of the GC-RD method was investigated during the method validation. The calibration curve was proved to be linear
(r=0.9986) in a wide concentration range (13–1000 ngeqv mL−1)
The lower limit of quantitation (LLOQ) was 13.7 ngeqv mL−1, and the limit of the detection (LOD) was 1 ngeqv mL−1.
Using this new GC-RD method, plasma levels of3H-labelled deramciclane and its metabolite were determined in dogs, after the administration of a single 10 mg kg−1 oral dose. Pharmacokinetic curves and the calculated pharmacokinetic parameters were compared to those obtained using a previously
elaborated gas chromatography-nitrogen selective detection method (GC-NPD) and to those obtained by measuring the plasma level
of total radioactivity (liquid scintillation counting, LSC). Pharmacokinetic curves and the calculated pharmacokinetic parameters
obtained with the two different gas chromatography detection methods (NPD and RD) showed good correlation. Comparison of these
results to those acquired by total radioactivity measurement demonstrated that deramciclane was intensively metabolised. Moreover,
the biological half-life (t
1
2/β
) of the unknown metabolites proved to be more than a magnitude longer than the half-life of the parent compound or that of
N-desmethyl metabolite.
Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997. 相似文献
28.
István Gyöngy 《Acta Appl Math》1994,35(1-2):165-177
We coasider a partially observable diffusion process (x
t,yt)t0 whose unobservable componentx
t lives on a submanifold M ofR
n
. We present some general conditions under which the conditional law ofx
t, given the observationsy
s
,s [0,t], admits a density w.r.t. a given measure on M. We characterize the analytical properties of this density by using appropriate Sobolev spaces.Research supported by the Hungarian National Foundation of Scientific Research No. 2290. 相似文献
29.
Rafael Abela Christopher Baines Xavier Donath Dierk Herlach David Maden Ivan D. Reid Dieter Renker György Solt Ulrich Zimmermann 《Hyperfine Interactions》1994,87(1):1105-1110
TheSR Facility Instruments presently available at PSI and the envisaged medium- and long-term developments are presented. The plans focus on further upgrades of the existing instruments and the development of new techniques using the very high fluxes becoming available at PSI, in particular the setup of a beamline with a fast kicker for muons on request (MORE) and the development of very low energy muon beams. 相似文献
30.
Gyrgy Frter 《Helvetica chimica acta》1974,57(1):172-179
A four step synthesis of Seychellene ( 1 ) is described. Intramolecular Diels-Alder reaction of dienon 2 furnished the tricyclic ketones 3 and 4 in good yield. Hydrogenation of 3 gave 5 and 6 . The higher reactivity of 6 with methyllithium compared to 5 allowed the selective preparation of 8 , which, on subsequent acid-catalyzed rearrangment afforded Seychellen in 57,5% yield. In an analogues manner epi-Seychellene was synthetized via the intermediates 5 and 7 . 相似文献