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1.
J. Umemura 《Journal of Molecular Structure》1977,36(1):35-54
Temperature dependence of the IR spectra of crystalline propionic acid were examined in the temperature range 242–50 K. The intensities of most absorption bands increased on lowering the temperature, but some bands diminished until they disappeared at temperatures lower than about 120 K. Normal coordinate analyses indicate that the former bands are due to the stable cis dimer and the latter due to the less stable trans dimer which would be produced from the cis dimer by simultaneous proton transfer along two hydrogen bonds. 相似文献
2.
Michael Bobik Friedrich Kohler Gustav Heger Hans Lischka Peter Schuster 《Chemical physics letters》1976,40(1):66-71
Measurements of dielectric permittivity and electric conductance are presented for mixtures of carboxylic acids — formic, trifluoroacetic, acetic and propionic — and non-polar liquids. For the dielectric and associative behavior of carboxylic acids a knowledge of the cis—trans conformational equilibria of the monomeric acid molecules seems to be essential. Therefore the cis and trans conformations of these molecules have been calculated by the CNDO/2 and PCILO methods. Appreciable rotational barriers for their interconversion have been obtained. 相似文献
3.
Federico Berti Cristina Forzato Giada Furlan Patrizia Nitti Giuliana Pitacco Ennio Valentin Ennio Zangrando 《Tetrahedron: Asymmetry》2009,20(3):313-321
The cis- and trans-4-benzylparaconic acids and their ethyl esters were synthesized with high enantiomeric excess by hydrolysis of the corresponding diastereomeric lactonic esters using α-chymotrypsin. Thus, at low conversion values, cis- and trans-4-benzyl-5-oxo-3-tetrahydrofurancarboxylic acids were separately isolated with 99% ee and 92% ee, respectively. Both ethyl ester diastereomers were also obtained in enantiopure form. The absolute configuration of the trans-lactonic acid was assigned by 1H NMR analysis of its ester derivatives with both enantiomers of 1-(9-anthryl)-2,2,2-trifluoroethanol, while that of the cis-lactonic acid was assigned by means of X-ray analysis of a crystalline derivative. The circular dichroism curves of the products obtained are also reported. 相似文献
4.
An INDO study has shown that the title compound exists in two diastereomeric propeller-like conformations, a cis form (C3 symmetry), and a trans form (C1 symmetry). The cis form is more stable than the trans form by 0·75 kcal/mole. The two forms undergo ready conformational interconversion by the two-ring flip mechanism, with activation energies of ca. 6 kcal/mole. 相似文献
5.
Calculations on performic acid at the 4-31G level, with and without bond functions with complete geometry optimization, and at the (9, 5) level, with and without polarization functions and rigid rotation, all give no sign of a well in the potential energy curve for rotation about the O/O bond axis in the region of 50° – 90° ; and all but the unaugmented 4-31G basis set find the cis-cis planar conformer to be the most stable form. Calculations at the (9,5) level with rigid rotation find the energies of the other planar conformers, relative to the cis-cis conformer, to be 0.94, 1.50 and 14.80 kcal mol?1 for the trans-trans, cis-trans and trans-cis structures respectively. These energies and also that for the barrier separating the cis-cis and cis-trans conformers, 1–2 kcal mol?1, are discussed in relation to corresponding data for formic acid, hydrogen peroxide and several planar four heavy-atom molecules. Dipole moment calculations using the same basis sets would seem to favor a skew conformation as the most stable for performic acid, but comparisons between calculated and experimental values for formic acid and for hydrogen peroxide cast doubt on the validity of such results. 相似文献
6.
At pH 5 (AcOHAcONa) protonation of the enamine of 3,6,6-trimethylnorpinane 2-one (3-methylnopinone) yields the cis immonium ion 6 (X OAc), which isomerizes to the thermodynamically more stable trans immonium ion 6′ (X OAc). Under more strongly acid conditions (aqueous hydrochloric or perchloric acids), the enamonium salts 7 (X Cl or ClO4) are formed; these isomerize, with a rate increasing with decreasing acidity to the cis immonium salts 6, stable under these conditions. Epimerization of the cis salt 6 (X Cl), occurs in ethereal hydrogen chloride, the rate increasing also with decreasing acidity. At pH 5, hydrolysis of the enamine yields 3-methylnopinone, the proportion of the less thermodynamically stable trans isomer increasing with a rise in reaction temperature. 相似文献
7.
The first total synthesis of the marine cyclopropane fatty acid (±)-17-methyl-trans-4,5-methyleneoctadecanoic acid was accomplished in eight steps and in 9.1% overall yield starting from 1-bromo-12-methyltridecane. The cis analog (±)-17-methyl-cis-4,5-methyleneoctadecanoic acid was also synthesized but in seven steps and in 16.4% overall yield. With the two isomeric cyclopropane fatty acids at hand it was possible to unequivocally corroborate the trans relative configuration of the naturally occurring fatty acid by gas chromatographic co-elution of the corresponding methyl esters. The cis isomer was cytotoxic to Leishmania donovani promastigotes with an IC50 of 300.2 ± 4.2 μM. 相似文献
8.
Ab initio calculations have been performed to determine molecular geometries, relative stabilities and the potential barrier of the fluoroacetyl fluoride molecule. The calculations indicate the existence of two stable conformations, trans and cis, in agreement with experimental studies. The potential barrier presents a maximum around 80° and an energy difference of ⋍ 17.5 kJ mol−1 with respect to the most stable conformer (trans). These calculations also confirm that this conformer is more polar than the cis form, with the total dipole moment oriented along the carbonylic bond. The intensity parameters of the trans and cis isomers in terms of their atomic polar tensors have been analysed using the “charge-charge flux-overlap” model. The calculations predict similar atomic polar tensors for both forms, suggesting practically equivalent electronic structures in the ground state. 相似文献
9.
Crystalline samples of cis- and of trans-o,o′-azodioxytoluene have been isolated. The cis crystals isomerize spontaneously to trans. IR spectra were recorded for the pure dimeric species as well as for o-nitrosotoluene and assignments of specific peaks were made. In solution the cis form is the energetically more stable species as revealed from NMR assignments on cis and trans samples. 相似文献
10.
Alexey A. Bazurin Tatiana A. Obuchova Angelina S. Danilova Konstantin V. Balakin 《Tetrahedron letters》2004,45(35):6669-6672
Several stereomerically pure amino acid derivatives containing the N-terminal trans-4-alkylcyclohexanoyl fragment were obtained. Hydrogenation of 4-alkylbenzoic acids in the presence of a special Ru-Ni/C catalytic system and isomerization of the resulting mixture of trans- and cis-isomers of 4-alkylcyclohexanecarboxylic acids were used as the key steps. The stereomeric configuration of all compounds was confirmed by 1H NMR spectroscopy. The compounds obtained possess a broad biological activity potential and are useful intermediates in the synthesis of stereomerically pure modified peptides. 相似文献
11.
DFT calculations have been performed for some Cu(III)-alkyl complexes. Complexes 1-19 were optimized to the square planar (sq) geometry and observed no imaginary frequencies. Although formally copper adopts d8 configuration (Cu(III)) in all the complexes, the Natural Population Analysis (NPA) revealed that the copper actually in d10 (Cu(I)) configuration, Bond order calculation suggested that the Cu(III)-Ettrans bond gets more bond order in the presence of poor π-acidic co-ligand (probe ligand). Relatively smaller bond order was calculated for Cu(III)-Mecis bond than Cu(III)-Ettrans bond and therefore Cu(III)-Ettrans bond is the strongest bond in all the complexes. Calculated less Chemical hardness (η) of complexes 1-19 suggested that all these complexes are less stable in nature. Energy Decomposition Analysis (EDA) revealed that the Cu(III)-Ettrans bond is relatively more stable than the Cu(III)-Mecis and Cu(III)-L (L = co-ligand/probe ligand) bonds. And also the Cu(III)-alkyl (Cu(III)-Mecis and Cu(III)-Ettrans) bond in complexes 1-17 is more of ionic in nature. However, Cu(III)-Ettrans bond is relatively more ionic than Cu(III)-Mecis bond. 相似文献
12.
The comparison was made of the dissociation degree values for the hydrogen-bond multimers of two geometrical isomers: cis- and trans-9-octadecenoic acids. The measurements were performed for the series of solutions of the discussed substances in the inactive solvents: carbon tetrachloride and n-hexane. The applied technique was ir absorption spectroscopy. The general statement is that trans-9-octadecenoic acid in both carbon tetrachloride and n-hexane shows greater tendency towards dissociation of multimers than cis-9-octadeconoic acid. 相似文献
13.
Esterification of cyclopentene, cyclohexene, cycloheptene and trans cyclooctene, with acetic, butyric and propionic acids, has been studied by a kinetic method. SnCl4 is the catalytic agent. SnCl4 undergoes a degradation which complicates the mathematical analysis of the reaction process. An appropriate mathematical method has been used. The experimental rate constant is connected with Hammett acidity function, H0, given by dissolution of SnCl4 in carboxylic acids: log k?ex,0 = ?H0 + δ. The kinetic isotope effects of solvent show that general acid catalysis is implied. A reaction mechanism has been put forward to explain every observed fact. The kinetic equation accounts for every mathematical implication of the mechanism. 相似文献
14.
The reduction of cis- and trans-6,6′-diethoxythioindigo (DETI) at a platinum electrode in N,N-dimethylformamide (DMF) solution was studied by cyclic voltammetry and controlled potential coulometry. The cis-form, produced by photoisomerization of the trans-form, is reduced at less negative potentials than the trans-. The trans-isomer produces a fairly stable radical anion upon one-electron reduction; the cis-radical anion isomerizes rapidly to the trans-form and also dimerizes much more rapidly than the trans-isomer. A photogalvanic cell based on this system was devised but showed low efficiency for conversion of radiant energy to electricity. 相似文献
15.
Robert Salle Quang-Tho Pham 《Journal of polymer science. Part A, Polymer chemistry》1977,15(8):1799-1810
Analysis by 250-MHz proton magnetic resonance (PMR) allows more precise examination of the microstructure of anionic polyisoprenes and polybutadienes obtained in the presence of organo-alkali metals. Besides vinyl addition, the propagation of contact ion pairs in dioxane solvent gives a mixture of cis and trans products with isoprene, whereas only trans product is obtained with butadiene. The presence of 1,4-trans-polyisoprene appears to be inconsistent with the cis configuration of the polyisoprenyllithium living end in dioxane or tetrahydrofurane media. In taking into account the existence of complexation phenomena, it was suggested that propagation mechanisms should involve a transition state which should begin with the trans configuration before isomerization into the more stable cis configuration. For the free ions, the living end of the carbanion should be entirely trans. 相似文献
16.
Sawang Loyarkat Benjamas Cheirsilp Kamontam Umsakul 《Applied biochemistry and biotechnology》2013,171(7):1726-1738
Several Clostridium spp. were incubated in a nitrogen-free medium (non-growth medium) containing only butyric acid as a sole precursor for performing butanol production by non-growing cells. Non-growing cells of Clostridium spp., especially Clostridium beijerinckii TISTR 1461, could convert butyric acid to butanol via their sole solventogenic activity. This activity was further enhanced in the presence of glucose as a co-substrate. In addition to glucose, other monosaccharides (i.e., galactose and xylose) and disaccharides (i.e., maltose, sucrose, and lactose) could also be used as a co-substrate with butyric acid. Among the organic acids tested (i.e., formic, acetic, propionic, and butyric acids), only butyric and acetic acids were converted to butanol. This study has shown that it is possible to use the non-growing cells of Clostridium spp. for direct conversion of sugars and organic acids to biobutanol. With this strategy, C. beijerinckii TISTR 1461 produced 12 g/L butanol from 15 g/L glucose and 10 g/L butyric acid with a high butanol yield of 0.68 C-mol/C-mol and a high butanol ratio of 88 %. 相似文献
17.
(?)-Cannabidiol has been synthesized from (+)-cis- and (+)-trans-p-menthadien-(2, 8)-ol-(1) and olivetol, using N, N-dimethylformamide dineopentyl acetal or weak acids, such as oxalic, picric, or maleic acid, as catalysts. Since the chirality of (+)-trans-p-menthadien-(2, 8)-ol-(1) is known, the above synthesis constitutes an unambiguous prove for the absolute configuration of (?)-cannabidiol and the two isomeric (?)-6a, 10a-trans-tetrahydrocannabinols. If stronger acids, such as p-toluenesulfonic, trifluoroacetic, or hydrochloric acid, are used as mediators for the reaction, (?)-Δ8-6a, 10a-trans-tetrahydrocannabinol is obtained as the main product. Transformation of the thermodynamically more stable Δ8-tetrahydrocannabinol into the less stable Δ9-isomer was achieved in a practically quantitative yield by addition of hydrochloric acid and elimination of the elements of hydrochloric acid by means of potassium t-amylate. If resorcinols I were used instead of olivetol in the condensation reaction with strong acids, the corresponding homologues of Δ8-tetrahydrocannabinol were obtained in varying yields. 相似文献
18.
Marian Mikoajczyk Barbara Ziemnicka Jan Krzywaski Marek Cypryk Bartomiej Gostyski 《Molecules (Basel, Switzerland)》2021,26(12)
Geometrical cis- and trans- isomers of 2-chloro-, 2-bromo- and 2-fluoro-4-methyl-1,3,2-dioxaphosphorinan-2-thiones were obtained in a diastereoselective way by (a) sulfurization of corresponding cyclic PIII-halogenides, (b) reaction of cyclic phosphorothioic acids with phosphorus pentachloride and (c) halogen–halogen exchange at PIV-halogenide. Their conformation and configuration at the C4-ring carbon and phosphorus stereocentres were studied by NMR (1H, 31P) methods, X-ray analysis and density functional (DFT) calculations. The stereochemistry of displacement reactions (alkaline hydrolysis, methanolysis, aminolysis) at phosphorus and its mechanism were shown to depend on the nature of halogen. Cyclic cis- and trans-isomers of chlorides and bromides react with nucleophiles (HO−, CH3O−, Me2NH) with inversion of configuration at phosphorus. DFT calculations provided evidence that alkaline hydrolysis of cyclic thiophosphoryl chlorides proceeds according to the SN2-P mechanism with a single transition state according to the potential energy surface (PES) observed. The alkaline hydrolysis reaction of cis- and trans-fluorides afforded the same mixture of the corresponding cyclic thiophosphoric acids with the thermodynamically more stable major product. Similar DFT calculations revealed that substitution at phosphorus in fluorides proceeds stepwise according to the A–E mechanism with formation of a pentacoordinate intermediate since a PES with two transition states was observed. 相似文献
19.
《Tetrahedron: Asymmetry》1998,9(12):2137-2154
Epimeric mannofuranose anomeric aminoesters are prepared from readily available azidolactones and can act as building blocks for the incorporation of mannofuranose units into peptide chains [carbopeptoids]; alternative acylating conditions allow either rapid acylation of the more stable but kinetically hindered amine or reaction with the less hindered but less stable amine to allow control of the anomeric configuration of the products. This is exemplified by coupling of the aminoesters with glycine derivatives to give dipeptide equivalents, and subsequent cyclization to spiro diketopiperazines. Anomers with the nitrogen function cis to the 2,3-diol are more stable than those with nitrogen trans; mannofuranose derivatives are more stable than the mannopyranose isomers. 相似文献
20.
Michel André Masson Alain Bouchy Jean Robert Dormoy Georges Roussy 《Journal of Molecular Structure》1981,74(1):11-17
The microwave spectrum of 2-furylisocyanate has been obtained in the frequency region from 8 to 40 GHz. This spectrum is attributed to the ground state of the cis and trans configurations. The rotational constants for both ground vibrational states have been determined. Two sets of vibrational satellites are observed and assigned to the modes of C-N torsion and CNC bending. The microwave results show and MINDO/3 calculations confirm that the barrier between the cis and trans conformers is high and that the cis conformer is more stable than the trans by 3 kcal mol?1. 相似文献