An efficient synthesis of 6-formyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acid and some carbonyl derivatives of it and its 6-acetyl homologue

Starting with 1,1-dimethoxy-2-propanone ( 1 ), 6-formyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acid ( 5a ) has been prepared in large quantities by a highly efficient, 4-step synthesis. This compound, along with its one carbon homologue, 6-acetyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acid ( 5b ) has been reacted with several carbonyl derivative forming reagents to provide a series of side chains for β-lactams. Among these carbonyl derivatives are styrylamides which were prepared from Wittig and Horner-Emmons reagents. The preparation of the phosphonium salts and phosphonate esters is also described.     

硫胺的燐光研究

硫胺无燐光，在碱中氧化后才产生燐光。 λ激发＝３００ｎｍ，λ发射＝４１０ ｎｍ，燐光寿命为１．３ｓ．硫胺燐光受溶剂极性影响甚小，１５种金属离子中只有铜离子可增强流胺燐光，寿命变短为 ０． ９４ ｓ，但不影响燐光光谱。在开始３０ｍｉｎ内有ＣｕＳＯ４的作用较快，以后逐渐变慢，到 ４ｈ后达平衡与不用ＣｕＳＯ４的燐光相近，启示ＣｕＳＯ４具有催化硫胺的氧化作用，建立了硫胺的燐光分析方法，用于两种维生素Ｂ１片的分析，分别为９８．５％与９８％。     

PA.FPNS: its synthesis and use in spectrophotometric determination of magnesium

A new polymeric chromogenic reagent PA.FPNS has been synthesized by condensing polyallylamine (PA) with 3-(4-formylphenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid (FPNS) and its properties studied. In alkaline media, PA.FPNS reacts with magnesium to form a water-soluble blue complex, whose absorption maximum is at 604 nm. The molar absorptivity (varepsilon) of the complex is 5.2 x 10(4)l mol(-1) cm(-1), which is four times that of the FPNS-Mg complex, and Beer's law is obeyed over the range 0-0.35 mug ml(-1) magnesium. Compared to the corresponding low-molecular-weight FPNS and other chromogenic reagents, PA.FPNS offers considerably improved sensitivity and selectivity for magnesium, which may be attributed to incorporating FPNS into a water-soluble polymer and the effect of the polymeric chain on the reaction microenvironment. Also, a simple and sensitive spectrophotometric method for the determination of magnesium has been developed and applied to water and human fluid samples with satisfactory results.     

Oligodeoxyribonucleotide analogues with bridging dimethylene sulfide,sulfoxide, and sulfone groups. Toward a second-generation model of nucleic acid structure

Short DNA analogues with bridging dimethylene sulfide, sulfoxide, and sulfone groups replacing the phosphate diesters (S-DNAs) were synthesized from building blocks prepared via two routes, both starting from D-glucose. Building blocks for RNA analogues were prepared by stereoselective introduction of nucleobase into a 2'-acylated ribose analogue. The ribose analogues were converted to deoxyribose analogues by replacement of a 3'-OH group by a thioacetyl unit, followed by photolytic deoxygenation or radical-based 2'-deoxygenation. DNA analogues joined via CH(2)(-)S-CH(2) units were prepared by S(N)2 displacement of a 6'-mesyl group on one building block using a thiolate nucleophile of another. 4,4'-Dimethoxytrityl protection and deprotection schemes were established for both the thiol and hydroxyl groups. The corresponding sulfoxide DNA analogues were obtained by oxidation with hydrogen peroxide. Sulfone DNA analogues were obtained by oxidation of the sulfide DNA with persulfate or hydrogen peroxide in the presence of a titanium silicate catalyst. The physical properties of several representative oligonucleotide analogues were examined, and interpreted in light of a "second-generation" model for DNA strand-strand recognition, a model that emphasizes the role of the polyanionic backbone in diminishing unwanted tendencies of highly functionalized molecules to form "structure" in solution. Even short sulfide-linked DNA analogues displayed association properties different from those displayed by standard DNA molecules. Complex formation observed with sulfide-linked tetramers by HPLC study in different solvents suggested that the complex is formed using hydrogen bonding. Sulfone-linked dinucleotides display Watson-Crick behavior; the tetramer, however, displayed self-structure. Self-structure and self-aggregation become more prominent as the length of the oligonucleotide analogues increases. The tendency to self-aggregate can be decreased by adding a charged sulfonate group to the 3'-end of the DNA analogue. Features of the second-generation model are important for many areas of nucleic acid chemistry, from the design of nucleic acid therapeutic agents to the search for life on other planets.     

Hydrogen bond studies: Part 118. A deuteron magnetic resonance study of BeSO4· 4D2O and Li2SO4· D2O

The electric field gradient (EFG) tensors at the deuterons in the water molecules in BeSO₄ · 4D₂O at 25°C are reported. The quadrupole coupling constants (e²Q/h) and asymmetry parameters (η) for the two independent deuterons are 181.1(4) and 194.8(3) kHz, and 0.226(4) and 0.123(3), respectively. The EFG tensor corresponding to the smallest e²qQ/h is considerably distorted by the beryllium ion, which causes a high η value as well as a deviation of the y-principal axis by 21.8(6)° from the normal to the water molecule plane. A redetermination of the EFG tensors at the deuterons in the water molecule in Li₂SO₄ · D₂O at 25°C and ?110°C is also reported. The e²Q/h and η values for the two deuterons are 236.6(1.2) and 239.8(1.1) kHz, and 0.091(8) and 0.126(7), respectively, at ?110°C. The corresponding e²qQ/h and η values for the averaged EFG tensor at 25°C are 125.8(1.1) kHz and 0.813(13), respectively. The results are in good agreement with those from the pioneer work by Ketudat and Pound, 20 years ago on the same compound.     

Inter- and intramolecular pathways for the formation of tetrahydrofurans from beta-(Phosphatoxy)alkyl radicals. Evidence for a dissociative mechanism

beta-(Phosphatoxy)alkyl radicals generated by photolysis of Barton PTOC esters in the presence of allyl alcohol and tert-butyl mercaptan undergo nucleophilic substitution followed by 5-exo-trig radical ring closure leading to tetrahydrofurans in good yield and with high trans selectivity. beta-(Phosphatoxy)alkyl radicals obtained by intramolecular hydrogen 1,5-abstraction with an alkoxyl radical undergo nucleophilic displacement providing tetrahydrofurans. The ensemble of results, including the effects of leaving groups and substituents, strongly support a dissociative mechanism for these radical nucleophilic displacement reactions.     

Stereoselektive Synthese einiger Amidester der (±)-erythro-2,3-Diphenylglutarsäure

Zusammenfassung Bei der Umsetzung von Methylphenylacetat mit Dialkylamiden der Zimtsäure in Gegenwart von NaNH₂ wurden Amidester der (±)-erythro-2,3-Diphenylglutarsäure hergestellt. Die Konfiguration der erhaltenen Verbindungen wurde durch Hydrolyse mit HCl (1:1) zu der entsprechenden Säure und im Falle der Umsetzung mit dem Zimtsäuredimethylamid durch eine mehrstufige Synthese aus demerythro-Säurenitril-ester festgestellt. Es wurden auch Bedingungen gefunden, unter welchen nur die Estergruppe hydrolysiert werden kann, wobei Mono-dimethylamid entsteht, das mit CH₂N₂ den Ausgangs-Amidester liefert.     

New 2D graphical representation of DNA sequences

We consider a 2D graphical representations of DNA sequences, which avoids loss of information associated with crossing and overlapping of the corresponding curve. We outline an approach, which is based on the construction of a three-component vector whose components are the normalized leading eigenvalues of the L/L matrices associated with DNA. The examination of similarities/dissimilarities among the coding sequences of the first exon of beta-globin gene of different species illustrates the utility of the approach.     

Molecular weight distribution studies. I. Radiation-induced polymerization of liquid α-methylstyrene

The concentration of water in purified and BaO-dried α-methylstyrene was found to be 1.1 × 10^?4M. The radiation-induced bulk polymerization of the α-methylstyrene thus prepared was studied in the temperature range of ?20°C to 35°C. The polymerization rate varied as the 0.55 power of the dose rate. The theoretical molecular weights and molecular weight distribution were calculated from a proposed kinetic scheme and these values were then compared with those found experimentally. The agreement between these two was reasonably close, and therefore it was concluded that, from the molecular weight distribution point of view, the proposed kinetic scheme for the cationic polymerization of α-methylstyrene is an acceptable one. The rate constant for chain transfer to monomer k_f changed with temperature and was found to be responsible for the decrease in the molecular weight of the polymer with increase in temperature. k_f and k_p at 20°C were found to be 0.95 × 10⁴ l./mole-sec and 0.99 × 10⁶ l./mole-sec, respectively.     

Synthesis and optical resolution of a series of inherently chiral calix[4]crowns with cone and partial cone conformations

A series of inherently chiral calix[4]arenes with cone and partial cone conformations and with crown ether moieties of variable size have been readily synthesized. By taking advantage of the carboxy appendage on the lower rim, these were condensed with the chiral auxiliary (S)-BINOL to form diastereomers which, in most cases, could be separated by preparative TLC, or more desirably, by column chromatography on silica gel (diastereomeric excess >99 % based on HPLC analysis). Seven enantiopure antipodes of inherently chiral calix[4]crowns were obtained after hydrolysis. It has been found that both the size of the crown moiety and alkylation of the last phenolic hydroxy group (accompanied with or without a change in the conformation) affect the separation of the diastereomers.