Stereoselective syntheses of (−)-chloramphenicol and (+)-thiamphenicol

Chloramphenicol and thiamphenicol have been enantioselectively synthesized using an asymmetric halohydrin reaction as a key step. In particular, halomethoxylation reaction was used, where O-methyl functions as a hydroxyl protecting group and eliminates an additional protection step.     

辅酶Ⅰ电化学配位反应机理的紫外光谱电化学研究

用薄层池原位紫外光谱电化学法研究了辅酶Ⅰ(NAD)在银电极上的电化学配位反应机理。实验结果表明：NAD能与溶出的银离子生成配合物，该配合物的配位反应是一种可逆过程，用光谱电化学的Nernst图解分析获得银离子与NAD配合物的主要存在形式是［Ag(NAD)₂］⁺，银离子是与NAD分子的腺嘌呤基团形成配合物的。配合物的银离子与银电极表面发生异相电子交换反应，该电化学反应是受吸附控制的准可逆电极过程。     

Use of NIRS technology with a remote reflectance fibre-optic probe for predicting major components in bee pollen

In the present work, we study the use of near infra-red spectroscopy (NIRS) technology together with a remote reflectance fibre-optic probe for determination of the major components in bee pollen. The method allows immediate control of the bee pollen without prior sample treatment or destruction through direct application of the fibre-optic probe to the sample.The regression method employed was modified partial least squares (MPLS). The calibration results obtained using 45 samples of bee pollen allowed the measurement of protein, moisture, ash, reducing sugars, and pH with multiple correlation coefficients (RSQ) and prediction corrected standard errors (SEPC) of 0.91, 0.56% for protein, of 0.78 and 0.49% for moisture; 0.92 and 0.049% for ash; 0.81 and 1.32 g of glucose/100 g of bee pollen; 0.84 and 0.15 for pH, respectively.The prediction capacity of the pattern was checked by applying it to samples of unknown pollen in external validation.     

Calculation of vertical ionization potentials of difluoramine by perturbation corrections to koopmans' theorem

The vertical ionization potentials of difluoramine are calculated by perturbation corrections to Koopmans' theorem. The calculation shows that difluoraimine has three overlapping bands between 15 and 16 eV. The calculated results compare well with the experimental values. The photoelectron spectrum of difluoramine is compared with that of OF₂ and CH₂F₂.     

Laser Raman spectroscopic study of photoreaction dynamics in p -chloro cinnamic acid crystal

Raman phonon spectroscopy has been used to study photodimerization reaction inp-chloro cinnamic acid (pCCA) crystal. The β-form of the crystal yields the 4,4′-dichloro-β-truxinic acid dimer. Six distinct low frequency phonon bands are observed in thepCCA monomer crystal. On reaction progress, these bands show a monotonic shift to lower frequencies and broaden out. Finally, in the dimer crystal the phonon spectrum shows two weak broad bands. These results suggest that the reaction is homogeneous in the initial stages and, as the product concentration increases, the lattice becomes highly disordered. The reactant and the product were characterised by infrared and Raman spectroscopy. The disappearance of aliphatic C=C bond stretching vibration and appearance of cyclobutane ring deformation and cyclobutane ring-breathing vibrations on reaction confirm photodimerization by cyclobutane ring formation. The large Stoke's shift between the absorption and emission band suggest strong exciton-phonon coupling in the monomer lattice. This reaction seems to be phonon-mediated.     

Transformations ofmyo-inositol hexa-O-nitrate under the action of amines

Reactions ofmyo-inositiol hexa-O-nitrate with ammonia and primary amines yield tetrahydroxy-1,4-benzoquinone derivatives,viz., its tetraammonium salt and its diimines, respectively. Reactions with secondary and tertiary amines give salts of rhodizonic acid, which are converted into salts of croconic acid under certain conditions. The reactions with secondary amines involve intermediate formation of radical species, which were dectected by ESR spectroscopy. A scheme for the chemical transformations ofmyo-inositol hexa-O-nitrate under the action of amines was proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2962–2967, December, 1996.     

A Zn(Ⅱ) 5-Aminoisophthalate Coordination Polymer

The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) (A),β = 109.187(2)o, V = 1482.6(2) (A)3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with Ⅰ ＞ 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel.     

Facile stereoselective synthesis of 1,3-disubstituted-4-trichloromethyl azetidin-2-ones

The highly stereoselective synthesis of 1,3-disubstituted-4-trichloromethyl azetidin-2-ones by the [2+2] cycloaddition of ketenes with imines derived from chloral is described.     

The six-membered annulation reaction involving sequential palladium-catalyzed allylic alkylation and Michael addition: scope and limitations

The palladium-catalyzed condensation of a variety of active methylene compounds with methyl 6-acetoxymethyl-hepta-2,6-dienoate was investigated. The six-membered adducts resulting from a η³ palladium complex alkylation-Michael addition sequence were obtained with moderate to good yields. In some cases, further evolution of the primary adduct was observed. The process has been expanded to access nitrogen heterocycles by using sodium p-toluenesulfonamide as the nucleophilic partner.     

Phase Selectively Soluble Dendritic Derivative of 4-(Dimethylamino)- pyridine: An Easily Recyclable Catalyst for Baylis-Hillman Reactions

Among the reactions in which C-C bonds are formed, the Baylis-Hillman coupling of aldehydes with α, β-unsaturated carbonylic compounds is currently attracting much interest due to the atom economy, the mild conditions and the generation of functional groups1,2. Furthermore, compared to the Heck, Suzuki and other palladium catalyzed C-C bond forming reaction3, the Baylis-Hillman reaction can be promoted by using organic bases in the complete absence of any metal4. However, almost all the …