SEARCH · USGS Science
Search indexed USGS publications on groundwater, aquifers, geologic maps, mineral resources and earthquakes. Explore source records by subject and place.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Studies related to the chemistry of aromatic fluorine compounds have been carried out at the Illinois State Geological Survey since 1933. In our reference collection we have several compounds that have not previously been described. This communication records data on 18 biphenyl, three terphenyl and some benzene fluorinated derivatives that were obtained as by-products and/or by specific synthesis. ?? 1973.
[No abstract available]
Three trifluorobenzenes were prepared by reaction of the corresponding trichlorobenzenes with potassium fluoride or pottassium fluoride-cesium fluoride mixtures in dimethyl sulfone. Molar yields were 12.8% for 1,2,3-, 8.3% for 1,2,4-, and 56.2% for 1,3,5-. Improved yields of the 1,2,3- (23.9%) and the 1,2,4- (34.0%) trifluorobenzenes were obtained from certain partially fluorinated intermediates. Several chlorofluorobenzene intermediates were obtained in goods yields by careful control of the reaction variables. The instability of the polyfluorobenzenes in the halogen-exchange reaction medium explains, in part, why only limited yields of the polyfluorobenzenes are obtained by using this method.
No abstract available.
Petrographic descriptions and electron microprobe analyses of minerals are presented for 35 specimens from seven suites chosen to examine the transition from magnetite series to ilmenite series granitoids along two transects across the Cretaceous-Paleocene Inner Zone batholith of southwestern Japan. Regularities in chemical compositions of amphiboles, biotites, and feldspars suggest that fundamentally similar processes produced the magmas that formed the two series. Constant or decreasing Fe/(Fe+Mg) for biotites and amphiboles with increasing host rock silica content, coupled with the absence of early formed magnetite and sphene, suggest that magnetite series rocks may have become oxidized during crystallization near the level of intrusion, through the processes of second boiling and differential loss of hydrogen. For the Daito-Yokota, magnetite series suite, Fe/(Fe+Mg) for biotites decreased from 0.48 to 0.37 as SiO 2 content of the host rock increased from 55.3 to 75.5 wt %; for an ilmenite series suite from the Takanawa Peninsula, Fe/(Fe+Mg) for biotites increased from 0.51 to 0.77 with an increase in host rock SiO 2 from 53.4 to 75.5. Detailed consideration of amphibole chemistry shows predominance of edenitic and tschermakitic substitution schemes as well as coupling between substitutions of Ti in octahedral sites and Al IV . Interrelations between amphibole and biotite chemistry show that Fe/(Fe+Mg) and Mn contents can be interpreted in terms of equilibration, whereas Ti content cannot. The chemistry of chlorites correlates well with that of biotites; primary and secondary muscovites are distinct in composition. Plagioclase in all studied suites shows igneous zoning appropriate to host rock composition; perthitic alkali feldspars in all samples have lost albite component, and temperatures based on the two-feldspar geothermometer are low. The biotite-apatite geothermometer is also inoperative for this group of samples because fully fluorinated apatites typically occur in biotites of modest F content. Whereas magnetites have reequilibrated, analyses of ilmenites for the representative Daito-Yokota and Takanawa suites corroborate biotite compositional data and suggest that f O2 probably differed by 2 to 3 orders of magnitude during crystallization of silica-rich magnetite and ilmenite series granites. Whole-rock chemistry supports mineral chemistry in suggesting that the studied granitoids have crystallized from magmas generated in a lower crustal environment in which mantle-derived magmas partially melted source materials with igneous characteristics.
The preparation of difluoropyridines by the Schiemann reaction was investigated. 2-Amino-6-fluoropyridine (IIIa), necessary for the synthesis of 2,6-difluoropyridine (IVa) by the Schiemann reaction, was conveniently prepared by the Curtius degradation of 6-fluoropicolinic hydrazide (IIa) and by the Hofmann reaction on 6-fluoropicolinamide (IId). Since an α -fluorine on a pyridine nucleus is preferentially replaced by hydrazine when it is either adjacent to or opposite a carbomethoxy group, the hydrazides necessary for the synthesis of 3-amino-2- and 6-fluoropyridine could not be prepared. These amines were prepared from the appropriate 2-fluoropyridinecarboxamide by the Hofmann reaction. The preparation of difluoropyridines was successful with two of the aminofluoropyridines and led to the following new compounds: 2,3-difluoro(IVb) and 2,6-difluoropyridine (IVa).
The α -halogenated pyridines react with potassium fluoride in various solvents to give replacement of the α -halogen by fluorine. A 50% yield of 2-fluoropyridine was obtained from 2-chloropyridine by heating with potassium fluoride in dimethyl sulfone or tetramethylene sulfone for twenty-one days; 2-bromopyridine gave a similar yield with a heating period of only seven days. The α -halogens of the polyhalopyridines undergo the exchange reaction more readily than do the halogens of the α -monohalopyridines. The proposed structures of the fluoropyridines are supported by alternate syntheses and by n.m.r. studies.