Reductive cleavage of axially disymmetric tertiary amines and quaternary ammonium salts by lithium aluminium hydride. Synthesis of new 1,1′-binaphthyl substituted amines

Axially disymmetric tertiary amines or quaternary ammonium salts $\text{A}$ are synthesized by double alkylation of primary or secondary amines with racemic or optically pure 2,2′-bis (bromomethyl)-1,1′-binaphthyl. Their reductive cleavage by lithium aluminium hydride in refluxing THF leads to chiral secondary or tertiary amines $\text{B}$, substituted by a binaphthyl unit, with high yields and absence of racemization.     

Structural studies of some body-centered cubic phases of mixed oxides involving Bi2O3: The structures of Bi25FeO40 and Bi38ZnO60

The structures of the compounds initially reported to be 7·Bi₂O₃·ZnO and 96·Bi₂O₃·4Fe₂O₃, have been determined by X ray methods. Three dimensional, absorption corrected diffractometer data were used and atomic parameters were refined by least-squares procedures. The structures are isomorphous, cubic witha = 10.194(3)and10.179(3)A?, respectively, and space group I23. Each Bi³⁺ ion is surrounded by five oxygen atoms that form an incomplete octahedral arrangement with BiO distances ranging from 2.07–2.60A?. The6s²inert electron pair completes the octahedron. The Bi³⁺ ions are vibrating anisotropically. Tetrahedral sites in the structures contain 61 and 46 electrons, respectively. These values are consistent with a statistical distribution of Zn²⁺ and Bi⁵⁺ ions or Fe³⁺ and Bi⁵⁺ ions on these sites. Molar ratios are derived that agree with the observed distributions of electron density and give rise to perfectly stoichiometric systems, devoid of cationic or anionic vacancies. The compositions studied correspond to Bi³⁺₂₄Bi⁵⁺Fe³⁺O₄₀ and Bi³⁺₃₆Bi⁵⁺₂ZnO₆₀ and they are optical enantiomorphs.It is proposed that a reduction in the percentage composition of Bi₂O₅ leads to metastable phases, in which all atomic positions remain fully occupied but some tetrahedral sites contain Bi³⁺ ions. The end product of the series is γ-Bi₂O₃ in which 50% of these sites contain Bi³⁺ and the remainder Bi⁵⁺ ions. We believe that γ-Bi₂O₃ is Bi³⁺₂₅Bi⁵⁺O₄₀.     

Folic acid analogs. Modifications in the benzene-ring region. 5. 2′,6′-diazafolic acid

The synthesis of 2′,6′-diazafolic acid was accomplished by the condensation of 2-acetylamino-4(3H)pteridinone-6-earboxaldehyde (XIV) with diethyl N-[(5-amino-2-pyrimidinyl)carbonyl]-L-glutamate (XIII) followed by reduction of the anil double bond and alkaline hydrolylic cleavage of the N²-acetyl and ethyl ester protecting groups. Intermediate XIII was prepared by starling with 5-nitro-2-styrylpyrimidine (VI) and proceeding via 5-arnino-2-styrylpyrimidine (IX). The henzyloxycarbonyl derivative of IX was prepared and oxidized to the corresponding 5-benzyloxycarbonylaminopyrimidine-2-carboxylic acid (XI). The coupling of XI with diethyl L-glutamate followed by hydrogenolysis of the henzyloxycarbonyl function afforded the desired intermediate XIII. 2′,6′-Diazafolic acid was a potent inhibitor of Streptococcus faecium and displayed marginal activity against leukemia 1,1210 in mice.     

Eine einfache Synthese chiraler Arylbenzochinone und Arylbenzohydrochinone; Versucheines NMR.-Nachweises von Chiralität in isopropylsubstituierten Benzalanilinen

Atropisomeric diphenyls (V and VI) are easily prepared by the acid catalysed condensation of 2-methoxycarbonyl-1,4-benzoquinone and 2-acetyl-1,4-benzoquinone and trimethyl-1,4-benzoquinone respectively with 2-isopropyl-5-methylanisole and 2-isopropyl-3,5dimethylanisole. The reaction is not affected by steric hindrance; the more highly substituted phenols gave better yields. One of the diphenylderivatives has been resolved with help of dehydroabietylamine. Thermodynamic data for the racemisation process have been determined by classical polarimetric techniques (Table 4). The chirality of most of the compounds prepared is easily detected by considering the signals of the diastereotopic isopropyl group in the NMR.-spectrum. Probably because of solvent interaction NMR. kinetics have failed to give information about the racemisation process. Isopropyl-substituted benzal-anilines have been prepared. They did not show any ‘splitting’ of the isopropyl-groups in the NMR.     

L3/L2 white-line intensity ratios in the electron energy-loss spectra of 3d transition-metal oxides

The L₃/L₂ white-line intensity ratio in transition-metal oxides deviates widely from the statistical value of 2 : 1 but shows interesting systematics. In a series of oxides of a given metal, the ratio reaches a maximum for the d⁵ configuration (e.g. MnO) and a minimum for the d⁰ configuration (e.g. KMnO₄). In a series of monoxides, sesquioxides and dioxides of different metals, the ratio is again a maximum at the d⁵ configuration and decreases as the configuration changes towards d⁰ or d¹⁰. Our results, obtained by electron energy-loss spectroscopy, carried out in an electron microscope, are interpreted on an atomic mechanism involving spin-spin coupling. According to this model, the L₂ transition probability decreases in the progression d⁰ to d⁵ whereas the L₃ transition probability decreases beyond d⁵.     

X-ray analysis of the influence of various nucleating agents on the crystallinity of poly-α-butene

The influence of various nucleating agents on the crystallinity of poly-α-butene form I has been studied. The nucleating agents were: adipic acid, salicylic acid, p-aminobenzoic acid, sodium benzoate and sorbic acid; their influences on the lattice parameters, degree of crystallinity, size of crystallites and texture have been examined. The analysis was carried out by wide-angle X-ray diffraction. The relative degrees of crystallinity in poly-α-butene samples containing nucleating agents were measured using the Hermans-Weidinger procedure; in order to obtain the size of crystallites, the Debye-Scherrer method was applied. The lattice parameters show no change but the relative degree of crystallinity, the size of crystallites and their texture depend on the nucleating agent used.     

Some biological transformations involving unsaturated linkages: the importance of charge separation and charge neutralization in enzyme catalysis

Current status of knowledge on the biological reduction of CC and CO is briefly reviewed. It is Argued that the crucial event in the reduction of CC is the addition of a proton to the more electron-rich terminal of the double bond to produce an electron-deficient species which is then neutralized through hydride transfer from NADPH. The activation for the reduction of a CO group may also be achieved by a related process in which the carbonyl oxygen is polarized by H-bonding to an acidic group on the enzyme, prior to hydride transfer from NAD(P)H.Thus with both these systems an early event in catalysis is the protonation of the substrate for which, normally, strong adds win be required. Since the groups available at the active-met of enzymes are weak acids, a mechanism through which powerful proton donating species could be transiently generated from them is proposed. The salient features of this mechanism may be enuinciatcd as follows: Let us consider the enzyme-substrate complex (A) in which an imidazolium group is about to play a role as a proton donating species. It is argued that rearrngement of initial complex(A)to the catalytic-complex(B), in which the negatively chared counter ion is removed away from the imidazolium cation, would transiently convert the latter group into a powerful proton danating species. the rearrangement (A)→(B) could occur through a protein conformational change or via a charge-relay system or a combination of both processes.     

Quantum mechanical scattering calculations on a spline-fitted ab initio surface: the He + H+2 (ν = 0, 1, 2) → HeH+ + H reaction

All-channel time-dependent quantum mechanical reaction probabilities are reported for the collinear He + H⁺₂(ν = 0, 1, 2) → HeH⁺ + H reaction at a total energy of 1.2 eV on previously reported diatomics-in-molecule (DIM) and spline fitted ab initio (SAI) surfaces. These results are in agreement with the previous quasiclassical trajectory results in that there is vibrational enhancement of the reaction probability on the SAI surface but not on the DIM surface. This agreement lends support to our previously drawn conclusion that small differences in the potential-energy surface can lead to substantially different dynamic results.