Purine Nucleoside Analogs. 12. Synthesis of Novel 8,9-Disubstituted Guanine Derivatives by S-Alkylation of 2-Acetamido-9-(2-acetoxyethoxymethyl)-6-oxo-8-thioxopurine

S-Alkylation of 2-acetamido-9-(2-acetoxyethoxymethyl)-6-oxo-8-thioxopurine was used to synthesize its novel S- and N₍₇₎-substituted derivatives. We have established the effect of the structure of the alkylating agent on the reaction conditions and its regioselectivity. We have shown that the synthesized guanine derivatives can be modified further.     

Trifluoroacetic acid: a more effective and efficient reagent for the synthesis of 3-arylmethylene-3,4-dihydro-1H-quinolin-2-ones and 3-arylmethyl-2-amino-quinolines from Baylis-Hillman derivatives via Claisen rearrangement

Trifluoroacetic acid has been discovered to be a highly effective and efficient reagent for the tandem Claisen rearrangement and cyclization reaction to yield 3-arylmethylene-3,4-dihydro-1H-quinolin-2-ones from compounds obtained from the S_N2 reaction between anilines and acetyl derivatives of Baylis-Hillman adducts of acrylates in the presence of DABCO. In contrast, similar compounds obtained from the acetyl derivatives of Baylis-Hillman adduct of acrylonitrile on treatment with trifluoroacetic acid directly furnish 3-arylmethyl-2-amino-quinoline via tandem Claisen rearrangement, cyclization and isomerization.     

The Substituent Effects of tert-Butyl Radical Addition to 2-Substituted Allyl Chlorides

The relative rates for the addition reactions of tert-butyl radical to 2-substituted ally chlorides I have een determined. The correlation of log k/k₀, vs. σ_m gives a ρ mvalue of 3.59 with correlation coefficient of 0.930. When the substituent CH₂Cl is excluded, correlation coefficient raises to 0.990 and ρ value becomes 3.39. The large p value and the deviation of relative rate of substituent CH₂C1 are discussed.     

Engineering cytochrome P-450s

Cytochrome P-450 isozymes represent a critical component of nature’s spectrum of detoxification catalysts that could be exploited for bioremediation. The ethanol-inducible human cytochrome P-450 2E1 serves as a model eukaryotic P-450 that complements the bacterial P-450 cam in dehalogenation and detoxification of environmental pollutants. We explored the construction of novel chimeric P-450s using cytochrome P-450 camC and 2E1 genes. For construction of chimera 1 (478 amino acids, 55.14 kDa), 145 amino acids from the N-terminus of P-450 2E1 protein (493 amino acids, 56.84 kDa) were replaced with 130 amino acids from the N-terminus of P-450 camC protein (415 amino acids, 46.66 kDa). In chimera 2 (525 amino acids, 60.24 kDa) the strategy involves replacement of 28 amino acids in the C-terminus of chimera 1 with 75 amino acids from the C-terminus of P-450 camC gene. Homology models of both the chimeric proteins were developed using SWISS-MODEL based on the known crystal structure of cytochrome P-450 camC, BM-3, 1DT6A, and 2C17A. The models indicated that the proposed heme-binding site was intact, which is inevitable for catalytic activity of cytochrome P-450s. The expression of chimera 1 and 2 genes in Escherichia coli DH5α was evident from light-pink cell pellets, protein band in sodium dodecyl sulfate polyacrylamide gel electrophoresis, and diagnostic carbon monoxide-difference spectra. Our studies show that strategies can be developed to exploit the natural diversity of the P-450 superfamily to generate chimeric biocatalysts that would provide new templates amenable to directed evolution.     

Vibrational spectra and conformations of 2- and 3-methylbicyclo[4.4.0]decanes

The conformations and heats of formation of all trans(T)- and cis(C)-2- and 3-methyl-substituted T- and Cbicyclo[4.4.0]decanes (BD) were calculated by the MM2 method of molecular mechanics. It was shown that the conformationally mobile T-2-Me-CBD and T-3-Me-CBD can exist in normal conditions as an inseparable mixture of conformers with a different equatorial or axial orientation of the Me groups. The Raman scattering (RS) spectra of TBD and CBD were investigated. RS bands whose frequencies were sensitive to the type of ring linkage and orientation (but not the position) of the Me substituents were detected in the 700–300 cm^–1 region.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2089–2097, September, 1992.     

Some developments in reaction and solution microcalorimetry,with particular reference to its use in biochemistry and cellular biology

The field of isothermal microcalorimetry as applied to systems of interest for aqueous solution chemistry, biochemistry and in cellular biology is briefly reviewed. Some techniques recently developed in the author's laboratory are described.     

Synthesis ofS-(+)-hydroprene

A novel path toS-(+)-hydroprene (1) starting from the technical gradeS-(+)-dihydromyrcene (2, e.e. 50%) is proposed. The latter was selectively transformed intoS-3,7-dimethyloctanal (5) in three steps including hydroalumination. The reactions of5 with allyl- or methallylmagnesium chloride followed, respectively, either by oxygenation in the presence of PdCl₂/CuCl or by ozonolysis, affordS,E-6,10-dimethyl-3-undecen-2-one (7) which was treated with ethoxyethynylmagnesium bromide to give the title juvenile hormone analogue in 23% overall yield.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 110–112, January, 1993.     

Correlation of the position of the bond functions in H-X with electronegativity

S type Gaussian bond functions are optimized for HF, H₂O, NH₃, and CH₄. The optimization is carried out with respect to the exponent and position in the H-X bond. The position is found to correlate well with the electronegativity of Pauling and Allred-Rochow.     

The use of “actinometer” gases in optical diagnostics of plasma etching mixtures: SF6-O2

The spectroscopic emission intensities from excited F atoms in SF₆-O₂ discharges at 1 torr have been correlated to the densities of atoms in their ground electronic state by measuring the excitation efficiencies of the electrons in the energy range 11 to 17 eV with a method which essentially consists in the analysis of the emission of Ar or N₂, added as actinometer gases to the discharge mixtures. The general applicability of the method has been tested by a direct titration of F atoms with chlorine. The spectroscopic analysis has allowed the determination of useful information on the trends of both the electron densities and their energies as a function of the oxygen percent in the feed.     

钌（Ⅱ）－联吡啶－巴比妥酸－Ce（Ⅳ）化学发光体系测定巴比妥酸的研究

利用巴比妥酸对Ｃｅ（Ⅳ）氧化钌（Ⅱ）－联吡啶化学发光反应的增强作用，建立了痕量巴比妥酸的自动脉冲注射化学发光测定法方法的检出限为１０×１０－９ｇ／ｍＬ，线性范围为５０×１０－８－６．２×１０－５ｇ／ｍＬ巴比妥酸的衍生物如巴比妥、苯巴比妥和戊巴比妥对Ｃｅ（Ⅳ）氧化钌（Ⅱ）联吡啶化学发光反应无增强作用据此对合成样中巴比妥酸作选择性检测探讨了巴比妥酸的增强机理