The synthesis of fused and spiro annulated carbohydrate structures using copper(I) catalysed intramolecular photoannulation of glucose derivatives

Intramolecular [2 + 2] photoannulation catalysed by copper(i)triflate has been applied to a series of carbohydrate derivatives obtained from glucose. Dienes 1a and 1b lead to cyclobutanes 3a and 3b whereas the diastereoisomeric dienes 5a and 5b gave diastereoisomeric products 7a and 7b. These results demonstrate that the reaction is stereospecific. Products 3a and 7a were converted into bromoesters 4 and 9 respectively. The Vasella elimination of 8 lead to the expected bicyclic aldehyde 10 and the ring expanded hydroxy ketone 12. The stereospecific formation of enantiomerically pure spiro annulated carbohydrates 18a and 18b was demonstrated whereas in example 19 no selectivity in the formation of 20 and 21 was observed.     

Mass and heat transfer effects in continuous production scale gas-liquid chromatographic equipment

Summary A study has been made of the temperature and related solute concentrations in a 12 column (7.6 cm OD×61 cm) sequential continuous chromatograph at feed rates of up to 1400 cm³hr^–1 of Arklone P-Genklene P. Moving the feed point from the middle of a column to the end cone was found to be particularly beneficial. Besides increasing throughput it enabled the system Arklone P and dichloromethane (separation factor 1.17) to be separated, not previously possible with a central feed point.     

Structure analysis of the propionic–pentafluoropropionic anhydride derivatives of norepinephrine and serotonin

Gas chromatographic/mass spectrometric analysis was used for the examination of norepinephrine and serotonin derivatives formed from their sequential reaction with propionic anhydride and pentafluoropropionic anhydride. The structures of the resulting derivatives were determined by the analysis of the mass spectra of the proteo and deutero homologs and by nuclear magnetic resonance spectroscopy. Mechanisms for the synthesis and electron impact fragmentation of these derivatives are proposed.     

The use of the doubly exponential distribution for tensile strength of rubbers

The doubly exponential (Fisher-Tippett Type 1) distribution has been assumed widely to represent the distribution of strength measurements and its use for tensile strength is recommended in BS 5324: 1976. This standard also recommends the use of a ‘mode’, calculated on this assumption, as the ‘most important measure of central tendency’ and indicates methods, previously described elsewhere in the literature, for calculating this mode.

In the present paper a much simpler and mathematically more rigorous method for calculating the ‘mode’ is described.

The use of the mode as a measure of central tendency is, however, debatable. The median conforms better with a key principle of control theory, namely equality of risk between manufacturer and purchaser. The median, unlike the mode, can also be estimated without bias directly from a comparatively small sample of measurements without any assumptions as to the population distribution.

Practical and theoretical evidence for the lack of general applicability of the doubly exponential distribution to strength measurements is presented.     

Simplex optimization of the synergic extraction of a bis-diketo copper(II) complex

Simplex optimization is used to maximize the synergic extraction of copper(II) acetylacetonate into cyclohexane through formation of the isoquinoline adduct. Concentrations of isoquinoline and acetylacetone and pH were optimized for 1 × 10^-4 M copper(II) solutions. Distribution coefficients of 0.25 were obtained above pH 7.9 for acetylacetone and isoquinoline concentrations above 3.0 × 10^-4 M and 2.0 × 10^-4 M, respectively.     

QCD analysis of non-singlet electromagnetic structure functions

A direct analysis of all data on the nonsinglet combination of electromagnetic structure functionsF ₂ ^p ?F ₂ ⁿ is shown to yield a value of the QCD scale-breaking parameter \(\Lambda _{\overline {{\rm M}S} } = 0.36 \pm 0.16\) Gev, in good agreement with that obtained from non-singlet neutrino data. The ratiod _v /u _v , extracted using the results of a previous neutrino analysis, shows an excess of up-quarks to down-quarks of about a factor of five at largex.     

New hypoxia-selective cytotoxines derived from quinoxaline 1,4-dioxides

A new series of quinoxaline 1,4-dioxides, structurally related to the benzotriazine tirapazamine 1 have been prepared starting from 5,6-dichlorobenzofuroxane 2 . The Beirut reaction between 2 and alkyl or aryl thiopropanones afforded the 2-methyl-3-alkyl(aryl)thioquinoxaline 1,4-dioxides 3a-3e . Selective oxidation of 3 with m-chloroperbenzoic acid yielded the sulphinyl 4a-4c and sulphonyl 5a-5b derivatives. Replacement of the sulphonyl group of 5a by chlorine or bromine gave 6 or 7 , while nucleophilic displacement by 3-(N,N-dimethylamino)propylamine afforded 8 . A dimer 9 was prepared from 5a and hydrazine hydrate. The methylthio group of 3a was replaced by using formamidine acetate giving the amino compound 10 . Bromination of the methyl group of 3b afforded 11 , which reacted with 2-aminoethanol giving 12 . Compounds were tested as cytotoxic agents both in oxic and in hypoxic cells.     

Residual photocurrent at a mercury electrode

The residual photocurrent observed at negative potentials with mercury in contact with slightly alkaline 1 M KCl solution has been reinvestigated and found to be caused partly by the reaction of e^?_aq with traces of unidentified electron acceptors and partly by reaction with the solvent. Such a solution can be freed from electron-accepting impurities by irradiation with light of shorter wavelength than 270 nm if SO^2?₃ is present at low concentration. The time constant for the homogeneous decay of e^?_aq at pH ca. 8.8 is then raised to about 400 μs. This slow decay is due to reaction with the solvent as the decay time constant can be increased considerably by raising the pH of the solution. In unsteady state experiments with purified 1 M KCl solutions of high pH containing no added scavenger for e^?_aq the current connected with electron emission and e^?_aq diffusion towards the electrode and the bulk of the solution, is cancelled out at ca. ?1.4 V vs. SCE by a thermal non-faradaic current component when 360 nm light is employed. When CO₂ is present at high concentration a similar cancellation is observed at lower pH at ca. ?1.1 V vs. SCE, suggesting a value for the diffusion coefficient of the radical-ion CO^?₂ about 3.3 times smaller than that of e^?_aq.     

Toward a general strategy for the synthesis of 3,4-dihydroxyprolines from pentose sugars

A general strategy is proposed, wherein a pentose sugar gamma-lactone can be converted, via a series of nine reactions, to a 3,4-dihydroxyproline, suitably protected for use in peptide synthesis. Thus, D-ribonolactone (6) has been converted to N-fluorenylmethoxycarbonyl-3,4-di-O-tert-butyldimethylsilyloxy-D-2,3-cis-3,4-cis-proline (7) in 18.9% overall yield. Likewise, L-arabinonolactone (11) has been converted to N-fluorenylmethoxycarbonyl-3,4-di-O-tert-butyldimethylsilyloxy-L-2,3-cis-3,4-trans-proline (36) in 13.7% overall yield and L-lyxonolactone (12) to N-fluorenylmethoxycarbonyl-3,4-di-O-tert-butyldimethylsilyloxy-L-2,3-trans-3,4-cis-proline (37) in 11.2% overall yield. These building blocks have also been fully deprotected to give the free amino acids. We believe that this series of reactions ought to be applicable to the synthesis of any of the eight stereoisomers of 3,4-dihydroxyproline, by judicious selection of the pentose starting material.