Phosphorylation of D-glucose derivatives with inorganic monoimido-cyclo-triphosphate

Phosphorylation of several D-glucose derivatives has been achieved using inorganic monoimido-cyclo-triphosphate (MCTP, Na(3)P(3)O(8)NH) in aqueous solution. In the phosphorylation of D-glucose, D-glucuronic acid, 2-deoxy-D-glucose and D-galactose, 1-O-diphosphoramidophosphono-beta-D-glucose, 1-O-diphosphoramidophosphono-beta-D-glucuronic acid, 1-O-diphosphoramidophosphono-2-deoxy-beta-D-glucose, and 1-O-diphosphoramidophosphono-beta-D-galactose were stereoselectively synthesized with yields of 54, 32, 37 and 46%, respectively. In the case of methyl alpha-D-glucoside, the phosphorylated products were methyl 3-O-diphosphoramidophosphono-alpha-D-glucoside and methyl 4-O-diphosphoramidophosphono-alpha-D-glucoside, and in the case of methyl beta-D-glucoside the products were methyl 2-O-diphosphoramidophosphono-beta-D-glucoside, methyl 3-O-diphosphoramidophosphono-beta-D-glucoside, and methyl 4-O-diphosphoramidophosphono-beta-D-glucoside. For D-mannose and D-allose, several phosphorylated products were obtained and the main products were 1-O-diphosphoramidophosphono-beta-D-aldoses.     

Phosphorylation of disaccharides with inorganic cyclo-triphosphate in aqueous solution

The phosphorylation of disaccharides by inorganic cyclo-triphosphate (P(3m)) with a six-membered ring was examined in aqueous solution. In the phosphorylation of cellobiose, lactose, and alpha,alpha-trehalose with P(3m), beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl 1-triphosphate, beta-D-galactopyranosyl-(1-->4)-beta-D-glucopyranosyl 1-triphosphate, and 3-O-triphospho-alpha-D-glucopyranosyl-(1-->1)-alpha-D-glucopyranoside were synthesized with maximum yields of 28%, 35%, and 20%, respectively. In the reactions of maltose and sucrose with P(3m), two phosphorylated products were obtained in yields of 42% and 58%, respectively. The main phosphorylated products were assigned to alpha-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl 1-triphosphate and beta-D-fructofuranosyl-(2-->1)-2-O-triphospho-alpha-D-glucopyranoside by heteronuclear multiple bond correlation (HMBC) NMR. The phosphorylation mechanism of disaccharides with P(3m) is discussed.     

Phosphorylation of 5'-deoxy-5-fluorouridine with inorganic phosphorylating agents

The phosphorylation of 5'-deoxy-5-fluorouridine (doxifluridine, 5'-DFUR) has been achieved using inorganic cyclo-triphosphate (P(3m), Na(3)P(3)O(9)) and monoimido-cyclo-triphosphate (MCTP, Na(3)P(3)O(8)NH) in aqueous solution. In the reaction of 5'-DFUR with P(3m), 2'-monophospho-5'-DFUR and 3'-monophospho-5'-DFUR were synthesized with a total yield of more than 95%. In the reaction of 5'-DFUR with MCTP, 2'-diphosphoramidophosphono-5'-DFUR and 3'-diphosphoramidophosphono-5'-DFUR were synthesized with a total yield of more than 40%. The phosphorylated products with P(3m) and MCTP were stable in neutral and alkaline solutions.     

How the shape of the NH2 group depends on the substituent effect and H-bond formation in derivatives of aniline

The geometry and electronic structure of the amino group in aniline and its derivatives are very sensitive to both intramolecular interactions such as substituent effects and intermolecular ones such as H-bonding. An analysis of experimental geometries retrieved from the CSD base and computational modeling of aniline and its derivatives and their H-bonded complexes by use of B3LYP/6-311+G** and MP2/aug-cc-pVDZ showed that the degree of pyramidalization of the amino group depends on H-bonding, which exists in two forms, (i) NH...B (base) and (ii) N...HB (Br?nsted acid), both of which affect the shape of the NH2 group. The effect may be significantly enhanced by a substituent through resonance interaction from electron-attracting substituents. The NH...B interactions lead to a substantial planarization of the group, whereas N...HB interactions do not. The natural bond orbital analysis allowed the authors to show that the changes in occupancy of the "lone pair" orbital and in geometry parameters describing pyramidalization of the group depend on the substituent constants.     

硝酸铷在醇水混合溶剂中的溶解度

本文通过简单精确的分析方法测定了硝酸铷在水、水＋甲醇以及在水＋乙醇中在不同温度下的溶解度。在甲醇和乙醇存在的情况下，硝酸铷在水的溶解度都明显降低。通过四参数方程对试验数据拟和，取得了满意的结果。同时也测定了三元体系在“饱和”和“非饱和”状态下的折光率，并对折光率和醇及盐的浓度进行关联。     

Polarity of para-disubstituted benzene derivatives: a correlation analysis of the substituent effect

Russian Chemical Bulletin - The article is concerned with the influence of resonance donor substituents RD on the dipole moments μ of molecules 1,4-RDC6H4RA containing resonance acceptor...     

Aminolysis of Y-substituted phenyl X-substituted benzoates with piperidine: effect of nonleaving group substituent

The title reaction has been suggested to proceed through a zwitterionic tetrahedral intermediate with a change in the rate determining step on the basis of the curved Br?nsted-type plots obtained. The curvature center of the curved Br?nsted-type plots is at pKa = 6.4 regardless of the electronic nature of the substituent X in the benzoyl moiety.     

A theoretical study of the anomalous substituent effect of the hydroxyl group

A theoretical study by MINDO/3 and STO-3G SCF calculations has been used to examine the effect of a H-bonded water molecule on the ability of the hydroxyl group to stabilise a carbocation centre. Alkoxy groups are better stabilising groups in the gas phase, hydroxyl is more effective in protic solvents.     

Benzimidazole derivatives. 4. The recognition of the voluminous substituent attached to the basic amino group of 5-HT4 receptor antagonists

We report a structure-affinity analysis of an important element in the pharmacophore model for the recognition of 5-HT4 receptor antagonists: the voluminous substituent attached to the basic nitrogen of the ligand. We have designed, synthesized and pharmacologically evaluated a series of benzimidazole derivatives 1 containing a common molecular skeleton formed by N-[(4-piperidyl)methyl]-6-chlorobenzimidazole-4-carboxamide and four different substituents (R = butyl, 2-[(methylsulfonyl)amino]ethyl, 5-[(phenylacetyl)amino]pentyl, and 5-[(benzylsulfonyl)amino]pentyl). These compounds possess binding affinities in the nM range (Ki = 0.11-1.50 nM). Moreover, a ligand that contains a hydrogen atom attached to the basic nitrogen (R = H; Ki = 150 nM) is used as a control for structure-affinity relationships.     

CH-stretching overtone spectra of a fast rotating methyl group: 2-CH3 and 2-CHD2 pyridines

The CH-stretching overtone spectra of the methyl group in gaseous 2-CH(3) and 2-CHD(2) methylpyridines are recorded with conventional Fourier transform near-infrared spectroscopy in the Deltav(CH) = 1-4 regions and by intracavity laser photoacoustic spectroscopy in the Deltav(CH) = 5 and 6 regions. All spectra exhibit a complex structure. They are analyzed with a theoretical model that incorporates, within the adiabatic approximation, the coupling of the anharmonic CH-stretch vibrations described by Morse potentials with the quasifree internal rotation of the methyl group and with isoenergetic combination states involving the six angle deformation modes of the methyl group. The molecular vibrations are calculated in terms of redundant internal coordinates in an unambiguous canonical form. A simultaneous analysis of different isotopic derivatives is thus achieved. The Fermi resonance coupling parameters are those previously determined for toluene. The technique of diabatic rotations is used to disentangle the multiple avoided crossings occurring along the internal rotation coordinate theta in the calculated spectra, which become rapidly very dense owing to the low symmetry of the system. This simulation is successful in reproducing the experimental spectra. In addition, the transferrability of the Fermi resonance coupling parameters between two parent molecules is demonstrated.     

Phosphorylation of trihydroxybenzenes with the trivalent phosphorus derivatives

Phosphorylation of the simplest trihydroxybenzenes and their acylated derivatives with the trivalent phosphorus reagents of cyclic and acyclic structure was discussed. A possibility of the selective phosphorylation of acylated trihydroxybenzene derivatives was demonstrated. A dismutation was detected, leading to dimers of the linear structure containing a variety of phosphorus-containing fragments of different nature.     

取代基对依布硒啉电子结构及光谱性质影响的理论研究

采用密度泛函理论B3LYP方法在6-311++G**水平对依布硒啉及其6个衍生物进行结构优化,并分析了取代基对分子几何构型、电荷分布、前线轨道能级分布的影响.在相同计算水平上采用含时密度泛函理论方法进行了电子光谱研究,讨论了取代基对电子光谱的影响.计算结果表明,标题化合物分子为非平面结构,苯并异硒唑酮环与苯环之间存在一...     

Theoretical study on the substituent effect of halogen atom at different position of 7-azaindole-water derivatives: relative stability and excited-state proton-transfer mechanism

We have theoretically investigated the substituted effect on the first excited-state proton-transfer process of nX7AI-H₂O (n?=?2~6, X?=?F, Cl, Br) complex at the TD-M06-2X/6-31?+?G(d, p) level. Here X is the substituted halogen atom, and n value denotes the substituted position of X, such as C₂, C₃, C₄, C₅, or C₆. For the substituted 7-azaindole clusters, 6X7AI-H₂O molecule is the most stable structure in water. The replacement of halogen atom X does not affect the characters of the HOMO and LUMO, but influence the S₀?→?S₁ adiabatic transition energies of nX7AI-H₂O (n?=?2~6, X?=?F, Cl, Br). Our calculated results show that the double proton transfer occurs in a concerted but asynchronous protolysis pathway no matter which H atom is replaced by halogen atom. The halogen substitution changes the structural parameters evidently and leads to amply the asynchronousity during the proton-transfer process. The ESPT barrier height increases or decreases due to the halogen atom and substituted position.     

The reaction of tetrakis(dimethylamido)titanium with self-assembled alkyltrichlorosilane monolayers possessing -OH, -NH2, and -CH3 terminal groups

The reactions of tetrakis(dimethylamido)titanium, Ti[N(CH(3))(2)](4), with alkyltrichlorosilane self-assembled monolayers (SAMs) terminated by -OH, -NH(2), and -CH(3) groups have been investigated with X-ray photoelectron spectroscopy (XPS). For comparison, a chemically oxidized Si surface, which serves as the starting point for formation of the SAMs, has also been investigated. In this work, we examined the kinetics of adsorption, the spatial extent, and stoichiometry of the reaction. Chemically oxidized Si has been found to be the most reactive surface examined here, followed by the -OH, -NH(2), and -CH(3) terminated SAMs, in that order. On all surfaces, the reaction of Ti[N(CH(3))(2)](4) was relatively facile, as evidenced by a rather weak dependence of the initial reaction probability on substrate temperature (T(s) = -50 to 110 degrees C), and adsorption could be described by first-order Langmuirian kinetics. The use of angle-resolved XPS demonstrated clearly that the anomalous reactivity of the -CH(3) terminated SAM could be attributed to reaction of Ti[N(CH(3))(2)](4) at the SAM/SiO(2) interface. Reaction on the -NH(2) terminated SAM proved to be the "cleanest", where essentially all of the reactivity could be associated with the terminal amine group. In this case, we found that approximately one Ti[N(CH(3))(2)](4) adsorbed per two SAM molecules. On all surfaces, there was significant loss of the N(CH(3))(2) ligand, particularly at high substrate temperatures, T(s) = 110 degrees C. These results show for the first time that it is possible to attach a transition metal coordination complex from the vapor phase to a surface with an appropriately functionalized self-assembled monolayer.     

Nucleophile-mediated ring expansion of 4-chloromethyl- and 4-mesyloxymethyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-ones to 6-tosyl-2,3,4,5-tetrahydro-1H-1,3-diazepin-2-ones: effect of the leaving group and the substituent at C6

A five-step synthesis of 4-chloromethyl- and 4-mesyloxymethyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-ones has been developed. The reaction of N-[(2-benzoyloxy-1-tosyl)ethyl]urea with sodium enolates of α-tosylketones followed by cyclization-dehydration, and debenzoylation gave 4-hydroxymethyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-ones, which were transformed into the 4-chloromethyl- or 4-mesyloxymethyl-derivatives. Treatment of the latter with nucleophilic reagents, such as sodium cyanide, sodium diethyl malonate, sodium thiophenolate, or potassium phthalimide, afforded the corresponding 4,7-disubstituted 6-tosyl-2,3,4,5-tetrahydro-1H-1,3-diazepin-2-ones as a result of ring expansion. The effect of the leaving group and the substitution at the position C6 on the reactivity of the pyrimidines is discussed.     

Features of the mass spectra of hetisine bases with an OH group at C-14

The EI mass spectra of five hetisine bases with an OH group at C-14 have been investigated. The main directions of fragmentation are initiated by the cleavage of the C-14-C-20 bond. With the aid of measurements of the elementary compositions of the molecular and fragmentary ions and of a comparison of the B/E linked-scanning and metastable defocusing spectra, the mechanism of the formation of the key fragments has been established and alternative methods for the production of certain ions have been revealed.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 82–89, January–February, 1992.     

Voltammetric oxidation of 2-oxo-1,2,3,4-tetrahydropyrimidin-5-carboxamides: substituent effects

Electrochemical oxidation of a series of 20 substituted 2-oxo-1,2,3,4-tetrahydropyrimidin-5-carboxamides (THPMs) in acetonitrile has been studied using voltammetric methods at a glassy carbon electrode to investigate the influence of the substituents on the 4- and 5-positions of the heterocyclic ring. Analysis of the results shows that the electronic nature and steric hindrance of the substituents, especially their orientations toward the heterocyclic ring, determine their effects on the oxidation potential. Analysis of the computational results obtained at the DFT-B3LYP/6-31++G** level of theory suggests a mechanism in which the first electron removal occurs from either the N(1) of the heterocyclic ring or N(17) of the amide substitution. This process is followed by a fast proton removal resulting in the formation of stable allylic and/or benzylic radicals which then undergo further oxidation to the 2-oxo-1,2-dihydropyrimidin-5-carboxamides (DHPMs).     

Preparation of CdS by thermal decomposition of double salts and saturated solutions of the systems Cd(HCOO)2-CS(NH2)2-CH3OH and Cd(CH3COO)2-CS(NH2)2-CH3OH

Summary The solubility isotherms of the systems Cd(HCOO)₂-CS(NH₂)₂-CH₃OH and Cd-(CH₃COO)₂-CS(NH₂)₂-CH₃OH have been investigated at 25°C. Reagents for the equilibrium existence of the salts Cd(HCOO)₂, Cd(HCOO)₂·2CS(NH₂)₂, CS(NH₂)₂, Cd(CH₃COO)₂, Cd(CH₃COO)₂·CS(NH₂)₂, and Cd(CH₃COO)₂·2CS(NH₂)₂ are found. The preparation of CdS by thermal decomposition of double salts and from saturated solutions by the dip technique are discussed.

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Herstellung von CdS durch thermische Zersetzung von Doppelsalzen und gesättigten Lösungen der Systeme Cd(HCOO)₂-CS(NH₂)₂-CH₃OH und Cd(CH₃COO)₂-CS(NH₂)₂-CH₃OH

Zusammenfassung Untersucht werden die Löslichkeitsisothermen der Systeme Cd(HCOO)₂-Cs(NH₂)₂-CH₃OH und Cd(CH₃COO)₂-CS(NH₂)₂-CH₃OH bei 25 °C. Die Kristallisationsfelder der Salze Cd(HCOO)₂, Cd(HCOO)₂·2CS(NH₂)₂, CS(NH₂)₂, Cd(CH₃COO)₂, Cd(CH₃COO)₂·CS(NH₂)₂ und Cd(CH₃COO)₂·2CS(NH₂)₂ werden bestimmt. Die Herstellung von CdS durch thermische Zersetzung von Doppelsalzen und gesättigten Lösungen anhand des Tauchverfahrens wird diskutiert.