The preparation of some reactive 1,6-disubstituted perfluorohexanes

Reactive 1,6-disubstituted perfluorohexanes have been prepared $\text{via}$ the reaction of 1,6-$\text{bis}$(dimethylhydrosilyl)-perfluorohexanes with alkyllithium and Grignard reagents. The resulting species may be derivatized in the same manner as organolithium reagents, but are appreciably more stable than the 1,6-dilithioperfluorohexane which is presumably generated by the halogen-metal exchange between an alkyllithium reagent and Br(CF₂)₆Br. 1,6-bis(Bromomagnesium)-perfluorohexane was also prepared in good yield by a halogen-metal exchange reaction.     

First Synthesis of 3-Mercapto-2(1H)-pyridinone, a Simple Disubstituted Pyridine Useful for Synthesis of the 4-Azaphenoxathiine Ring System and Its Novel Diazaphenoxathiine Analogs: 1,6-Diazaphenoxathiine and 2,6-Diazaphenoxathiine(1)

3-Mercapto-2(1H)-pyridinone (1) can be synthesized in three simple high-yielding steps from readily available 2-tert-butylthiazolo[4,5-b]pyridine (2). Its disodium salt condenses with o-chloronitrobenzene, 2-chloro-3-nitropyridine, and 3-chloro-4-nitropyridine 1-oxide to give respectively 4-azaphenoxathiine (10), 1,6-diazaphenoxathiine (12), and 2,6-diazaphenoxathiine 2-oxide (14) which reduces to 2,6-diazaphenoxathiine (15). The structures of these previously unreported azaphenoxathiine systems were confirmed by assignment of their respective (13)C NMR spectra.     

Growth and decay tables for radium-225 and actinium-225

To facilitate the use of²²⁵Ra as a yield tracer in radiochemical assays of²²⁶Ra and²²⁸Ra, growth and decay tables for²²⁵Ra, and its daughter²²⁵Ac, have been computed.     

Observations on the reduction of aryl nitro groups with palladium-sodium borohydride

The reduction of aryl nitro groups by the palladium-sodium borohydride system can be controlled in some instances to give products differing from those of catalytic hydrogenation. With six equivalents of borohydride added to the catalyst 2,2′-dinitrobiphenyl formed only 2,2′-diaminobiphenyl. With added sodium hydroxide and varying amounts of borohydride and catalyst, the reduction can be controlled to give benzo[c]cinnoline, benzo[c]cinnoline 5-oxide or benzo[c]cinnoline 5,6-dioxide. In a closed system, the reagents reduce both the nitro and olefin functional groups in 6-nitro-5,8-dimethoxy-1,4-dihydro-1,4-ethano-naphthalene. In an open flask flushed with argon, the reduction is confirmed to the nitro group. Reduction of 2-chloro and 4-chloronitrobenzene with palladium-borohydride gives substantial yields of the appropriate chloroanilines. In contrast, hydrogen and palladium give aniline as the major product from each of these. These results suggest that the addition of sodium borohydride to palladium on carbon produces a reductive entity differing from that of catalytic hydrogenation.     

Self-repairing polymers: poly(dioxaborolane)s containing trigonal planar boron

The molecular weight of poly(dioxaborolane)s can be controlled during the polymerization reaction or through post-polymerization processing in such a manner that hydrolytic damage to these materials may be repaired, thereby regenerating the polymer.     

OZONE, MIDDLE ULTRAVIOLET RADIATION AND THE AQUATIC ENVIRONMENT

Marine organisms in the upper layers of the sea may be endangered by increased ultraviolet radiation resulting from declines in the thickness of stratospheric ozone. Evidence supporting this hypothesis includes the fact that wavelengths of potentially damaging ultraviolet radiation can penetrate to ecologically significant depths and laboratory findings that many marine organisms are extremely sensitive to this radiation. Estimated effects of increased ultraviolet radiation on populations of marine organisms range from insignificant to catastrophic. Direct estimation of population effects have not been made, although this is the only adequate measure of the potential impact. The extreme diminution of ozone during the Antarctic spring, coupled with the dynamics of phytoplankton production in this region, may provide conditions suitable for an environmental test of the hypotheses that marine organisms are endangered by reduced stratospheric ozone. There is an urgency to the testing of this hypothesis since these populations may be directly impacted at the present time.     

The crystal and molecular structure of dodecafluorotriphenylene, C18F12

The dodecafluorotriphenylene molecule is considerably distorted from planarity by steric interactions between the “ortho” fluorine atoms which approach to within 2.41 Å of each other (or about 0.3 Å closer than the sum of the van der Waals radii for two fluorine atoms, 2.70 Å).     

A solar erythemal (sunburn) radiation dosimeter

Measurement of solar erythemal radiation is a technically demanding task because it is accompanied by a vastly greater flux of other solar radiation. An inexpensive solar erythemal radiation dosimeter has been designed which is based on the photocleavage of an alkyl disulphide. The reaction is carried out in a hydrocarbon solvent which can readily donate hydrogen atoms and as a result no polysulphides with absorptions in the erythemal action spectrum were formed. This avoided non-linearities in the dosimeter arising from inner filtering effects. The amount of alkylthiol produced as a result of exposure of the corresponding dialkyl disulphide solution to solar erythemal radiation was linearly related to the dose of radiation received.     

Analysis of the pungent principles of ginger and grains of paradise by high-performance liquid chromatography using electrochemical detection

Summary The pungent principles of ginger and grains of paradise are examined using a reversed-phase HPLC column. An electrochemical detector is used to selectively detect the phenolic gingerols and shogaols. The retention indices of the compounds are compared using methanowater and acetonitrile-water as eluents.Presented at the 14th International Symposium on Chromatography London, September, 1982