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1.
M. I. Batuev A. A. Akhrem A. D. Matveeva I. N. Nazarov 《Russian Chemical Bulletin》1958,7(11):1341-1344
Summary The cis-configuration of 1-acetyl-2-methylcyclohexanol exists in the form of the predominant ae conformation; the trans-configuration in the form of the ee conformation. 相似文献
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We have studied the base-promoted heterocyclization of alkyl N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)carbamates and N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamides, investigating the effect of the nitrogen protecting group and the relative configuration of the leaving group at C3 and C4 on the outcome of this reaction. We have observed that the sodium hydride-promoted heterocyclization of alkyl N-(cis-3,trans-4-dibromocyclohex-1-yl)carbamates (10, 12, 14, 16, 18) is a convenient method for the synthesis of 7-azabicyclo[2.2.1]heptane derivatives. For instance, the reaction of tert-butyl N-(cis-3,trans-4-dibromocyclohex-1-yl)carbamate (10) with sodium hydride in DMF at room temperature provides 2-bromo-7-[(tert-butoxy)carbonyl]-7-azabicyclo[2.2.1]heptane (2) (52% yield), whose t-BuOK-promoted hydrogen bromide elimination affords 7-[(tert-butoxy)carbonyl]-7-azabicyclo[2.2.1]hept-2-ene (31) in 78% yield, an intermediate in the total synthesis of epibatidine (1). However, the NaH/DMF-mediated heterocyclization of alkyl N-(trans-3,cis-4-dibromocyclohex-1-yl)carbamates (11, 13) is a more structure dependent reaction, where the nucleophilic attack of the oxygen atom of the protecting group controls the outcome of the reaction, giving rise to benzooxazolone and 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives, respectively, from low to moderate yields, in complex reaction mixtures. Conversely, the NaH/DMF heterocyclizations of N-(cis-3,trans-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamide (40) or N-(trans-3,cis-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamide (42) are very clean reactions giving 7-azabicyclo[2.2.1]heptane or 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives, respectively, in good yields. Finally, a mechanistic investigation, based on DFT calculations, has been carried out to rationalize the formation of the different adducts. 相似文献
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This article reviews the present status of the application of transient or time-resolved Raman spectroscopy to the mechanistic studies of the cis—trans photoisomerization in conjugated molecules. Attention is focused on the vibrational information about the molecular structure of the electronically excited intermediates which are involved in the process of photoisomerization. Two examples, the trans to cis photoisomerization of stilbene through the lower excited singlet state and the cist to trans isomerization of retinal through the lowest excited triplet state, are included. 相似文献
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Abstract In this communication we wish to report an interesting case of the isolation and characterization of the cis and trans isomers of 1-(p-bromobenzylidene)-2-indanone and their ketals. Prior to this work, Hoogstreen and Trenner2 had reported on the cis and trans isomers of 1-(p-chlorobenzylidene)-2-methyl-5-methoxyindenylacetic acid. The condensation of 2-(N-morpholinyl)-indene (1, prepared by the reaction of 2-indanone3 and morpholine) with P-bromobenzaldehyde was conducted by refluxing them in the presence of acetic acid for 4 hours. Acid hydrolysis of the reaction mixture followed by dry column chrcmatography over sillica gel using a fraction collector afforded two iscmeric monobenzylidenes, compounds 2(36.6%, mp 110–111°)and 3(1.3%, mp 115–116°) and a dibenylidene, compound 4 (8.7%, mp 205°). The relative rations of the mono- and dibenzylidenes seemed to depend on the reaction conditions. Higher yields of the monobenzylidenes 2 and 3 were obtained by conducting the reaction in the presence of UV light. The structures of these monobenzylidenes were established as cis and trans isomers of 1-(p-bromobenzylidenes)-2-indanone on the Basis of elemental analyses and ir and nmr spectroscopy. The ir spectra4 (CHCl3) of compounds 2 [1725 (c=0), 1620 (c=c)cm?1] and 3[1710 (c=o), 1570, 1600 (c=c) cm?1] were consistent with the structures. The molecular ion peaks as well as the fragmentation patterns in the mass spectra of both these compounds were consistent with the assigned structures. Before going into the omr discussion it should be pointed out that treatment of compound 2 with athylene glycol in the presence of p-toluene sulfonic acid produced two ketals, 5 (38.3% mp, 118–120°) and 6 (30.6% mp, 125–126°). As depicted; the ketals 5and 6 were also found (by omr) to be related to each other as cis and trans isomers. Furthermore, each of them could be hydrolyzed with acid to the corresponding monobenzylidenes 2 and 3 without any isomerization. However, UV irradiation of compounds 2 and 3 gave equilibrium mixtures containing both the isomers, indicating isomerization had occurred under photolytic conditions. 相似文献
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Automated determination of fatty acid methyl ester and cis/trans methyl ester composition of fats and oils 总被引:1,自引:0,他引:1
de Koning S van der Meer B Alkema G Janssen HG Brinkman UA 《Journal of chromatography. A》2001,922(1-2):391-397
The determination of the fatty acid composition (as methyl esters, FAMEs) of fats and oils and their cis/trans (CTME) distribution requires a simple, but manual and time-consuming sample preparation. The so-called BF3 method is often the preferred procedure. Because FAME/CTME analyses are encountered very frequently in the food industry, an automated, robot-based alternative is proposed which uses the sodium methylate procedure. After sample weighing and the (manual) addition of heptane (2 min), a XYZ robotic autosampler is used for all remaining work, which includes reagent addition, agitation, sample settling and the final injection into the gas chromatograph (10 min). The performance of the sodium methylate and BF3 methods are compared by analysing some 30 oil and fat samples. The novel procedure is much faster (less than 15 min versus ca. 1 h) and manual sample handling is drastically decreased. The experimental results obtained with the two methods frequently are the same, while small differences can be explained by (known) differences of the two methods in the conversion of minor oil/fat constituents, such as free fatty acids, wax esters and sterol esters. In case of FAME analyses, a hot injection is to be preferred over a cold injection. The RSDs of the peak areas were 1.5% for the major fatty acids to 11% for peaks that were just above the noise level. The detection limit were approximately 0.03%. 相似文献
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Smith K Liu CH El-Hiti GA Kang GS Jones E Clement SG Checquer AD Howarth OW Hursthouse MB Coles SJ 《Organic & biomolecular chemistry》2005,3(10):1880-1892
Bromine has been added to cis,trans,trans-1,5,9-cyclododecatriene under various reaction conditions. All expected direct addition products have been isolated, and their structures have been determined by microanalysis, NMR and X-ray crystallography. Advanced NMR techniques were used to determine solution conformations of several of the compounds, enabling comparison with the solid-state conformations obtained by crystallography. 相似文献
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The Stereoselective synthesis of cis and trans 2-methyl-1-phenyl-3-azabicyclo[3.1.0]hexanes and 1,2-diphen-yl-3-azabicyclo[3.1.0]hexanes from 2-oxo-1-phenyl-3-azabicyclo[3.1.0]hexane is described. The relative stereochemistry of the products was established by nuclear magnetic resonance and molecular modeling studies. 相似文献
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The kinetics of the ruthenium-promoted cis,cis to trans,trans isomerization of 1,1,2,2,5,5,6,6-octamethyl-1,2,5,6-tetrasilacycloocta-3,7-diene were investigated. Incubation of a ruthenium alkylidene complex, (Cy(3)P)RuCl(2)(==CHPh)Ru(p-cymene)Cl(2), in CD(2)Cl(2) for 5 days at 40 degrees C afforded a catalytically active ruthenium species that was shown to be responsible for promoting the isomerization. The isomerization was observed to proceed in two steps: (1) conversion of the starting cis,cis isomer to a proposed cis,trans intermediate and (2) subsequent conversion of the intermediate to the product trans,trans isomer. Kinetic studies demonstrated that the two steps are first-order with respect to the concentrations of the cis,cis isomer, the intermediate, and the ruthenium alkylidene complex. The data were further consistent with a mechanism involving bimolecular hydride addition-elimination during the two isomerization steps. 相似文献
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A Raman scattering study of the v3 vibration—rotation band in methyl iodide as a function of temperature and dilution (in cyclohexane) has been performed. All the data satisfy the second moment criterion. Detailed information about rotational correlation function, angular velocity correlation function, various correlation times and mean-square torque has been obtained. The correlation function, in the pure liquid, decays slowly with decrease in temperature whereas it decays faster with decreasing concentration in cyclohexane. It has been shown, from a consideration of the second moment as a function of concentration, that the contribution of collision-induced scattering to the v3 band of methyl iodide is negligible. Applicability of a simple “damped librator model”, with a view to understanding certain aspects of the rotational motion in methyl iodide, is discussed. 相似文献
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HPLC-separation of cis and trans monounsaturated fatty acids 总被引:1,自引:0,他引:1
Summary The chromatography of monounsaturated fatty acids as their methyl esters on silver nitrate-loaded HPLC-columns has been studied. The separation of cis- and trans-isomers was easily achieved even with columns of low performance. High-performance small-particle-columns treated with silver nitrate separated a large variety of monounsaturated cis and trans positional isomers. The influence of variable silver-loads on the selectivity of the system was studied and a survey of the distribution of positional trans C181 isomers in commercial margarines is given. 相似文献
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A detailed account is given of the experimental approach to measuring transient spectra of dilute gases using picosecond pulses. The picosecond continuum generated by Nd:glass laser pulses is used to probe gaseous samples and spectra are recorded in a double beam arrangement. The pump and probe pulses interact with the sample over a few centimeters by means of a dielectric waveguide. Picosecond time resolved spectra, relative fluorescence quantum yield measurements, and fluorescence spectra are reported for trans-stilbene under collision free conditions. The lifetime of the optically prepared states at 265 nm and 287 nm are 15 ps and 55 ps respectively, measured by the decay of the transient absorption. The deuteration effect is less than 20%. The variation of the fluorescence yield with vibrational energy excess in the excited state of trans is fitted to these lifetime measurements to yield the variation of nonradiative decay due to twisting of trans-stilbene. Cis-stilbene is suggested to twist in less than 1 ps. Consideration of the spectral results yields new information about the isomerization of stilbene, in particular that there exists a barrier to twisting in the isolated molecule and that vibrational energy redistribution at the trans configuration is probably not complete on the time scale of our experiments. A pictorial model for discussing constant energy relaxation phenomena is introduced. 相似文献
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Braun M Hessamian-Alinejad A de Lacroix BF Alvarez BH Fischer G 《Molecules (Basel, Switzerland)》2008,13(4):995-1003
The novel 3H-spiro[1-benzofuran-2-cyclopentan]-3-one skeleton has been made accessible by different routes. One- and two-step protocols lead to tricyclic and tetracyclic benzofuranones 2 and 3, respectively. A four-step synthesis to spirocompound 4 is described. The novel spirocyclic benzofuranones display modest to no inhibition of the human peptidyl prolyl cis/trans isomerase Pin1. 相似文献
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T. M. Filippova S. D. Mikhno N. S. Kulachkina I. M. Kustanovich V. M. Berezovskii 《Chemistry of Heterocyclic Compounds》1971,7(3):290-293
The PMR and proton magnetic double resonance (PMDR) spectra were obtained for five cis and trans isomer pairs of substituted 4-amino-3-hydroxythiophanes. A comparison of the PMR parameters of the cis and trans isomers made it possible to formulate the characteristic differences in their spectra. On the basis of the data obtained, the trans configuration is proposed for the ethoxycarbonylamino and hydroxy groups in 4-ethoxycarbonylamino-3-hydroxy-3-cyanothiophane, the configuration of which has not been previously determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp.316–319, March, 1971. 相似文献
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B. V. Unkovskii T. D. Sokolova Yu. F. Malina K. I. Romanova 《Chemistry of Heterocyclic Compounds》1973,9(12):1501-1506
The cis and trans isomers of 3-methyl-1-tert-butyl-4-acetyl- and 3-methyl-1-tertbutyl-4-carbomethoxy-4-piperidols, the three-dimensional configurations of which were established by means of their IR and UV spectra, were synthesized in order to study the interrelationship between the structure and reactivity of stereoisomeric piperidines.Translated from Khimiya Geterotsiklicheskikh Soedinenni, No.12, pp. 1659–1665, December, 1973. 相似文献