Effects of stereoisomerism in the mass spectra of 2,4-disubstituted thiacyclohexanes

The mass spectra of cis- (Ia-c) and trans-2-methyl-4-R-thiacyclohexanes (IIa-c; a R = n-C₄H₉, b R = n-C₅H₁₁, c R = Ph) were studied. It was established that [M-CH₃]⁺ ions, which correspond to the loss of a methyl group from the 2 position, are formed more readily in the case of the less stable trans isomers IIa-c than in the case of cis isomers Ia-c. The three-dimensional structures of the substances have no effect on the degree of elimination of the R substituent. The relative ionization energies (RIE) for Ia,b and IIa,b and the relative appearance energies (RAE) of the [M-CH₃]⁺ ions were measured by the electron impact method. It was found that the RIE are almost 0.05 eV lower and that the RAE of the [M-CH₃]⁺ ions are 0.1 eV lower for trans isomers IIa,b than for cis isomers Ia,b.Communication 4 from the series Ionization and appearance energies in organic chemistry, See [1] for Communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 333–338, March, 1981.     

Mass-spectrometric study of the fragmentation of stereoisomeric forms of 2-(4′-alkoxycarbonylbuly)-3-hydroxy-4-ureidotetra-hydrothiophene under electron impact

The dependence of the characteristic fragmentation under electron impact on the spatial orientation of the substituents of cis and trans isomers of 2-(4-alkoxycarbonylbutyl)-3-hydroxy-4-ureidotetrahydrothiophenes was studied. The possibility of the identification of these isomers on the basis of the intensity ratios of the peaks of the ions formed via two competitive fragmentation pathways with splitting out of the substituents from the C₍₃₎ and C₍₄₎ positions was demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 455–459, April, 1984.     

Synthesis of β-substituted tetrahydrofurans by the prins reaction

Mixtures of 3-trif uoroacetoxy- and 3-chloro-4-alkyltetraliydrofurans were synthesized by the reaction of a series of-olefins with formaldehyde in trifuoroacetic acid and trimethylchlorosilane.The characteristics of the mixtures of cis and trans isomers are given, and the n_D ²⁰ values are given for the trans isomers.Bashkir State University, Institute of Fine Organic Synthesis. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 605–608, May, 1995. Original article submitted November 4, 1994; revision submitted May 10, 1995.     

Synthesis,structure and stereochemistry of diiodide complexes (E)[(η5-t-BuC5H3)Fe(CO)2I]2 (E = Me2Si,Me2SiSiMe2, and Me2SiOSiMe2)

Reactions of diiron complexes (E)[⁵-t-BuC₅H₃)Fe(CO)]₂(-CO)₂ [E = Me₂Si (1), Me₂SiSiMe₂ (2), and Me₂SiOSiMe₂ (3)] with iodine in CHCl₃ yielded diiodide complexes (E)[⁵-t-BuC₅H³)Fe(CO)₂I]₂ [E=Me₂Si (5), Me₂SiSiMe₂ (6), and Me₂SiOSiMe₂ (7)]. Like (1–3), complexes (5–7) also exists as mixtures of cis and trans isomers even though the Fe–Fe bond in (1–3) has been cleaved. When the pure isomers (1–3) reacted with iodine respectively in CHCl₃, the cis isomers (1c–3c) yielded only the cis products (5c–7c), whereas the trans isomers (1t–3t) yielded only the trans isomers (5t–7t). This indicates that iodination of bridged diiron complexes is stereospecific. Similar treatment of trans-(Me₂Si)[{⁵-t-(heptyl)C₅H₃}Fe(CO)]₂(-CO)₂ (4t) with iodine gave only the trans product (Me_2Si)[{⁵-t-(heptyl)C₅H₃}Fe(CO)₂I]₂ (8t). The molecular structure of (5t) was determined by X-ray diffraction.     

Theoretical study of isomerism in protonated forms of N2O,NPO, and P2O

The geometric parameters of the isomers HN₂O⁺, HPNO⁺, and HP₂O⁺ were calculated by the nonempirical SCF/3-21G* method and their relative energies were determined with consideration of the electronic correlation in the MP3/DEHD + PS approximation. According to the calculations, protonation of N₂O, PNO, and P₂O molecules should preferably take place at the oxygen atom. Isomers with a quasilinear NNO and PNO backbone are most advantageous in HN₂O⁺ and HPNO⁺, and cyclic isomers are 60 and 30 kcal/mole less stable, respectively. On the contrary, the cyclic form is more stable for HPO ₂ ⁺ (by 10 kcal/mole). The bond at the attacked atom usually weakens (breaks) and the neighboring (opposite) bonds are strengthened in protonation. Protonation of P₂O stabilizes the cyclic isomer by 15 kcal/mole more strongly than the "open" isomer, resulting in inversion of their position on the energy scale. In the case of N₂O and PNO, the relative position of the cyclic and basic isomers virtually does not change, but the linear NPO isomer is destabliized. The stability of the cyclic isomers in comparison to the "open" isomers increases on substitution of N atoms by P atoms in both molecules of N₂O, PNO, and P₂O and in their ions HN₂O⁺, HPNO⁺, and HP₂O⁺. This tendency probably holds in subsequent transition to As and Sb atoms.Institute of New Chemical Problems, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 126–134, January, 1992.     

Investigation of the stereochemistry of N-substituted 2,5-dimethyl-4-piperidinones by NMR spectroscopy

The conformations of the cis and trans isomers of N-substituted 2,5-dimethyl-4-piperidinones were studied by means of the¹H and¹³C NMR parameters. It was established that in the case of bulky and electron-acceptor substituents attached to the N atom the cis isomers are virtually completely represented by the chair (2a,5e) conformation, while the trans isomers are characterized by the chair (2e,5e) twistboat (2a,5e) chair (2a,5a) conformational equilibrium. It is demonstrated that 1-tert-butyltrans-2,5-dimethyl-4-piperidinone hydrochloride has the twist (2a,5e) conformation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1760–1768, August, 1990.     

Vibrational spectra and structures of the cis and trans isomers of linear benzindigo

The resonance Raman and IR spectra of the cis and trans isomers of linear benzindigo were investigated, and the frequencies of the vibrations of the multiple bonds were assigned. The large splitting of the frequencies of the symmetrical (_s) and asymmetrical (_as) vibrations of the carbonyl groups of the trans isomer of benzindigo and indigo is associated with the electronic interaction of these groups in the process of vibration.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 501–504, April, 1981.     

13C NMR spectra and three-dimensional structures of isomeric 3,4-substituted thiophans

The chemical shifts and the direct carbon-proton spin-spin coupling constants for a number of cis and trans isomers of 4-amino-substituted 3-hydroxy(acyloxy)-thiophans, the configurations of the substituents in which and the conformational states were previously established by an independent method, were studied. It was found that in the spectra of the cis isomers the signals of the vicinal ¹³C atoms, which bear the substituents, are shifted to strong field as compared with the trans isomers ( trans-cis 1.7–4.3 ppm). Conformational effects of the substituents on the chemical shifts of the ring ¹³C atoms were noted. It is shown that a relationship exists between the direct carbon-proton spin-spin coupling constants and the spatial orientations of the acyloxy and acylamino substituents for five-membered saturated rings.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1612–1616, December, 1981.     

Kinetics of solid-phase ligand-substitution reactions in diammine(1,4,8,11-Tetraazaundecane)chromium(III) bromide isomers

The kinetics of solid-phase reactions of substitution of coordinated ammonia by outer-sphere bromide ions in [CrL(NH₃)₂]₂Br₃·nH₂O, where L is 1,4,8,11- tetraazaundecane, n 2–2.5, was studied by a nonisothermal method by differential thermogravimetry, mass spectrometry, and investigations in a flow-type reactor. The kinetic stability of the isomeric salts increases in the series trans相似文献   

含绿色荧光蛋白发色团双自由基分子的非线性光学性质

采用密度泛函理论(DFT)方法研究了系列含绿色荧光蛋白发色团双自由基分子光学异构体的几何结构、极化率(αs)和第一超极化率(βtot).结果表明,引入电子给受体取代基使分子的极化率增大,而对第一超极化率有不同影响.对于光照前的反式结构,引入电子受体βtot值增加,且βtot值随取代基吸电子能力的增强而增大;引入电子给体βtot值降低,且βtot值随取代基给电子能力的增强而减小.当分子变成相应的顺式结构时,其βtot值变化趋势与反式结构的结果正好相反.光异构化前后分子的βtot值变化不同,引入电子受体使顺式结构的βtot值比反式结构的小,其中―NO2使顺式结构的βtot值减小为反式结构的1/6;引入电子给体使反式结构的βtot值比顺式结构的小,其中―NH2使反式结构的βtot值减小为顺式结构的1/6.从而,光异构化起到调节非线性光学(NLO)响应的作用.     

Conformation analysis of diphosphine

Extended basis set ab initio computations are performed on HF, PNO-CI and CEPA level to determine the structure of P₂H₄ and the potential curve E() for rotation around the P-P axis. The structure parameters are optimized for dihedral angles of 0 ° (cis), 50 °, 80 ° (gauche or semi-eclipsed), 130 °, and 180 ° (trans). It turns out that P₂H₄ has a gauche equilibrium structure, a local minimum for trans which is 2.5 kJ/mol above gauche, a rather large cis barrier of 20 kJ/mol and a gauche trans barrier of 3.5 kJ/mol. The potential E() is extremely flat in the region 50 ° < < 310 °, where E() varies by less than 5 kJ/mol. Electron correlation tends to reduce the barriers but has no drastic effect on E().     

Aryloxydihydropyrans. XII. Configuration and conformations of 8-(3,4-dihydro-2-pyranyloxy)quinoline derivatives

The configuration and conformations of stereoisomeric 4R-8-(3,4-dihydro-2-pyranyloxy)quinolines were studied by means of their PMR spectra. It was established that the trans isomers of the investigated compounds have primarily a half-chair conformation and display an anomeric effect. A sofa conformation is proposed for the labile cis isomers.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 607–610, May, 1976.     

Aziridinyl ketones and their cyclic anils. 6. Proton-acceptor capacities of aziridinyl ketones

The proton-acceptor capacities of a number of cis- and trans-aziridinyl ketones were estimated by IR spectrometry from the shifts of the OH bands of phenol, p-bromophenol, and trichloroacetic acid.It is shown that the cis isomers interact with all of the proton donors, whereas the trans isomers interact only in CCl₃COOH.The latter is due to the fact that a strong intramolecular hydrogen bond exists in the trans-NH-aziridinyl ketones, whereas considerable steric hindrance to complexing develops in the trans-N-alkylaziridinyl ketones.It was established that the formation of complexes takes place at the carbonyl group of the aziridinyl ketones.See [1] for Communication 5.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1641–1644, December, 1981.     

Capillary electrochromatographic enantioseparations using a packed capillary with a 3 microm OD-type chiral packing

A technique for separating methyl esters of monounsaturated fatty acids by argentation chromatography using silver nitrate-impregnated TLC plates is described. Monounsaturated fatty acid methyl esters are separated from polyunsaturated and saturated fatty acid methyl esters and the monounsaturated fatty methyl esters are resolved according to chain length. cis isomers are well resolved from the corresponding trans isomers. R(F) values for individual monounsaturated fatty acids are very reproducible. The potential of the technique in metabolic studies is demonstrated in the chain elongation of [14C]-18:1(n-9) and delta-9 desaturation of [14C]-18:0 by human skin fibroblasts. Recoveries of individual [14C]-fatty acids for scintillation counting exceed 94%.     

Electronic structures of the S2O and S3 isomers: an ab initio CI study

The electronic structures of the S₂O and S₃ isomers have been dealt with by the multireference double-excitation (MRD) configuration-interaction (CI) calculations, using contracted [5s3p1d] and [4s2p1d] basis functions for the S and O atoms, respectively. The ground-state geometries for the SOS (symmetric chain), S₂O (symmetric ring) and SSO (unsymmetric chain) are optimized, and their vertical singlet excitation energies are calculated. It is found that SSO is the most stable of the three isomers and that the ground state (¹A₁) of the S₂O (ring) is correlated with the excited states of SOS (2¹A₁) and SSO (3¹A). The chain and ring isomers of S₃ have been treated in a similar manner. Energetics for the ring closure of the O₃, SO₂, SSO and S₃ chain molecules are discussed on a unified ground.Dedicated to Professor J. Koutecký on the occasion of his 65th birthdayPresented at the 5th International Congress on Quantum Chemistry, Montréal, August 1985     

Stereochemistry of nitrogen heterocycles. 68. Stereochemistry of 2,5-dimethyl-4-piperidone, 2,5-dimethyl-4-piperidol,and their N-benzoyl derivatives

The isomers of 1-benzoyl-2,5-dimethyl-4-piperidone were obtained and equilibrated (89.8% cis 10.2% trans isomer, preferred conformations 2a, 5e, and 2a, 5a). The position of the equilibrium between the isomers of 2,5-dimethyl-4-piperidone was determined by two independent methods (89.5% trans 10.5% cis isomer). The differences in the free energies of the isomers, the conformational energy of the -CH₃ group, and the energy of syn-axial 1,3-interaction between the CH and the unshared electron pair were calculated; the decrease in the conformational energy of the -methyl group in the series of piperidine (1.6), 4-piperidone (1.47), and N-acyl-4-piperidone (1.28 kcal/mole) was explained by the successive weakening of the repulsive interaction between the -CH₃ group and the n-pair of the nitrogen as a result of the flattening of the ring and of the conjugation between the free electron pair of the nitrogen and the electrons of the acyl carbonyl group. The last previously unknown fourth isomer of 2,5-dimethyl-4-piperidol, which exists in the 2e,4a,5a conformation, was obtained by the reduction of cis-1-benzoyl-2,5-dimethyl-4-piperidone followed by debenzoylation. In contrast to the secondary amine, its N-benzoyl- and N-benzyl-substituted derivatives exist in the alternative 2a,4e,5e conformation. The configurations and conformations of the isomers were determined by means of the IR and NMR spectra.For Communication 67, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 953–961, July, 1989.     

New method for the reduction of benzofurans

A new method for the reduction of benzofurans with potassium and sodium borohydrides in CF₃COOH was developed. It is shown by gas-liquid chromatography and PMR spectroscopy that mixtures (23) of the cis and trans isomers of dihydro derivatives of benzofuran are formed in the reduction. The mechanism of the reduction includes intermolecular transfer of a hydride ion to the protonated form of the benzofuran.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1174–1176, September, 1981.     

Thin layer chromatographic studies of anils II. Separation,identification and determination

Thin layer chromatographic behaviour of ten anils was studied on silica gel adsorbent mixed with starch binder with ten solvent systems. Simultaneous separation, identification and determination of ternary mixtures of isomers was stressed. TheR _F increasing order was found to be dependent on the solvent and independent of the degree of saturation of the chamber. The correlations ofR _F with _max and (C=O) of isomers were established and used in their identification. Six anils were separated in methanol—benzene (11).