Photophysics and photochemistry of sterically strained α-haloanthraquinones: The bromo and/or chloro substituted compounds

The steric hindrance between the oxygen and halogen atoms results in the structural deformation of α-haloanthraquinones and their lowest excited triplet (T₁) states are of mixed nπ ^*-ππ ^* or ππ ^* character with unusually short lifetimes. Moreover, the rates of hydrogen-atom abstraction from ethanol by the T₁ states decrease with their increasing ππ ^* character, and the proximity of the halogen atom to the hydroxy group causes the photochemical intramolecular elimination of hydrogen halide from the initial photoproducts (α-haloanthrahydroquinones) yielding α-haloanthraquinones (or anthraquinone) with one less halogen atom than the original molecule; the final product is anthrahydroquinone. The remarkably large structural deformation of 1,8-dihaloanthrasemiquinone radicals which gives rise to the simultaneous formation of 1,8-dihaloanthrahydroquinones and the original anthraquinones. Of particular interest is observation of the absorption band(s) attributable to the second excited triplet (T₂) states of 1,8-dihaloanthraquinones. However, the electron transfer from triethylamine (TEA) to these T₂ states generating the radical anions is observed only in acetonitrile, while that to the T₁ states generating their exciplexes with TEA is observed not only in acetonitrile but also in toluene and ethanol.     

The reactions of iminosulfur difluorides and chlorine monofluoride

The reactions of perfluoroalkyl- and perfluoroacyl-iminosulfur difluorides with chlorine monofluoride result in the preparation of perfluoroalkyldichloroamines and a new class of compounds N,N-dichloroperfluoroamides, R_fC(O)NCl₂, via the elimination of SF₄. The amides, FC(O)NCl₂ and CF₃C(O)NCl₂, in addition to 1,2-bis-(dichloroamino)tetrafluoroethane, Cl₂NCF₂CF₂NCl₂, are reported and characterized. The reactions of CIF with other sulfur(IV) imines proceed in an analogous manner to form perfluoroalkyl-dichloroamines via the elimination of the corresponding sulfur(IV) fluoride.     

S-4-methylphenyl-o,o-bis[1-benzotriazolyl] phosphorothioate: a versatile phosphorylating agent

The phosphorylating agent obtained by treatment of S-4-methylphenyl phosphorodichloridothioate with 1-hydroxybenzotriazole can not only be applied for the introduction of polyphosphate functions at the terminal ends of nucleic acids, but also for the formation of 3′-5′-phosphotriester linkages.     

Analogs of pyrimidine nucleosides

α-(1-Cytosinyl)-γ-butyrolactone was obtained by condensation of bis(trimethylsilyl)cytosine with α-bromobutyrolactone. The reduction of α-(1-cytosinyl)-γ-butyrolactone with sodium borohydride gave N₁-(1,4-dihydroxy-2-butyl)cytosine, the acylation of which with benzoyl chloride and subsequent partial hydrolysis gave N₁-(1,4-dihydroxy-2-butyl)-N₄-benzoylcytosine.     

Rapid analysis of small glass fragments by atomic-absorption spectroscopy

A rapid method is described for the determination of magnesium, iron and manganese in small glass fragments (250-500 mug). The speed of the analytical procedure is made possible by the use of a convenient cold digestion stage allied to a discrete sampling method which permits the three elements of interest to be determined by flame atomic-absorption spectrophotometry.     

Crystal and molecular structure of 1-aza-6′-(3′-oxo-5′, 5′-dimethyl-δ1′-pyrrolin-3′-yl)methylidene-2,2,7,7-tetramethyl-4-hydroxybicyclo-[2.2.21azaoctane

An x-ray structural study has shown that 6-(3-oxo-5,5-dimethyl-¹-pyrrolin-3-yl)methylidene-2,2,7, 7-tetramethyl-4-hydroxybicyclo[2.2.2]azaoctane is formed as a low-molecular-weight byproduct of the solid-phase polymerization of 1,4-bis(2,2,6,6-tetramethyl-4-hydroxy-4-piperidyl)butadiyne.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 585–587, March, 1990.     

Dioxane analogs of flavylium salts

The synthesis of benzodioxane derivatives of 1-benzopyrilium salts is reported and their reaction with nucleophiles is investigated.Taros Shevchenko University, Kiev 252017. Translated from Khimiya Geterotsiklicheskikb Soedinenii, No. 3, pp. 322–324, March, 1995. Original article submitted February 6, 1995.     

Arsenic speciation by capillary gas-liquid chromatography

Specific environmentally significant arsenic compounds are determined by capillary gas-liquid chromatography. Inorganic (arsenite, arsenate) and organic (monomethylarsonate, dimethylarsinate) arsenicals are measured as the corresponding methylthioglycolate derivatives, which are simultaneously separated on wide-bore borosilicate glass and fused-silica columns under conditions of temperature programming. Inorganic arsenate and arsenite cannot be differentiated by the derivatization technique. Flame-ionization and electron-capture detection are evaluated. A simple and rapid sample preparation procedure is used for water, urine, blood, and tissue.     

Convenient method for preparation of esters of N-carbonyl-α-amino acids

Conclusions A convenient method was proposed for obtaining the esters of N-carbonyl--amino acids, which is based on the reaction of the esters of N-trimethylsilyl--amino acids with phosgene in the presence of a tertiary amine.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1682–1684, July, 1977.     

Internal molecular disorder in the nematic and smectic phases of thermotropic liquid crystals studied by NMR SPDE experiments

The recently developed NMR SPDE experiment is shown to provide a new and particularly convenient technique for probing the conformational dynamics of mesogens in thermotropic liquid crystals. Measurements have been made in the nematic and smectic phases of the 4,4′-di-n-alkoxyazoxybenzenes. It is shown for the first time that the internal disorder of the alkyl end chains is intimately related to the molecular organization of these mesophases.