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51.
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53.
Peter Ettmayer Johann Waldhart Alfred Vendl 《Monatshefte für Chemie / Chemical Monthly》1979,110(5):1109-1112
X-Ray studies of the mixed nitride phases indicate complete miscibility in all cases. Lattice parameters generally showed negative deviations from the additivity rule.
Teilauszug aus der Dissertation des Dipl.-Ing.J. Waldhart an der Technischen Universität Wien, Österreich. 相似文献
54.
The FAKE method of approximate molecular-orbital calculations is presented and illustrated by application to a number of molecules. The method is of the extended Huckel type but uses accurately computed kinetic-energy matrix elements and avoids scale factors of the Wolfsberg—Helmholtz type. It also includes neighbor-atom charge effects and single-center off-diagonal matrix elements. These features permit FAKE occupied-orbital energies and charge distributions to come into close agreement with corresponding ab initio quantities. 相似文献
55.
56.
Syntheses of Sulfonated Derivatives of 4-Amino-1, 3-dimethylbenzene and 2-Amino-1, 3-dimethylbenzene Direct sulfonation of 4-amino-1, 3-dimethylbenzene (1) and sulfonation of 4-nitro-1,3-dimethylbenzene ( 4 ) to 4-nitro-1,3-dimethylbenzene-6-sulfonic acid ( 3 ) followed by reduction yield 4-amino-1,3-dimethylbenzene-6-sulfonic acid ( 2 ). The isomeric 5-sulfonic acid ( 5 ) however is prepared solely by baking the acid sulfate salt of 1 . Reaction of sulfur dioxide with the diazonium chloride derived from 2-amino-4-nitro-1,3-dimethylbenzene ( 7 ) leads to 4-nitro-1,3-dimethylbenzene-2-sulfonyl chloride ( 8 ), which is successively hydrolyzed to 4-nitro-1,3-dimethylbenzene-2-sulfonic acid ( 9 ) and reduced to 4-amino-1, 3-dimethylbenzene-2-sulfonic acid ( 6 ). Treatment of 4-amino-6-bromo-1,3-dimethylbenzene ( 12 ) and 4-amino-6-chloro-1, 3-dimethylbenzene ( 13 ), the former obtained by reduction of 4-chloro-6-nitro-1,3-dimethyl-benzene ( 10 ) and the latter from 4-chloro-6-nitro-1, 3-dimethylbenzene ( 11 ), with oleum yield 4-amino-6-bromo-1,3-dimethylbenzene-2-sulfonic acid ( 14 ) and 4-amino-6-chloro-1,3-dimethylbenzene-2-sulfonic acid ( 15 ) respectively; subsequent carbon-halogen hydrogenolyses of 14 and 15 lead also to 6 (Scheme 1). Baking the acid sulfate salt of 2-amino-1, 3-dimethylbenzene ( 17 ) gives 2-amino-1, 3-dimethylbenzene-5-sulfonic acid ( 16 ), whereas the isomeric 4-sulfonic acid ( 18 ) can be prepared by either of the following three possible pathways: Sulfonation of 2-nitro-1,3-dimethylbenzene ( 20 ) to 2-nitro-1,3-dimethylbenzene-4-sulfonic acid ( 21 ) followed by reduction or sulfonation of 2-acetylamino-1,3-dimethylbenzene ( 19 ) to 2-acetylamino-1,3-dimethylbenzene-4-sulfonic acid ( 22 ) with subsequent hydrolysis or direct sulfonation of 17 . Further sulfonation of 18 yields 2-amino 1,3-dimethylbenzene-4,6-disulfonic acid ( 23 ), the structure of which is independently confirmed by reduction of unequivocally prepared 2-nitro- 1,:3-dimethylbenzene-4,6-disulfonic acid ( 24 )(Scheme 2). 相似文献
57.
Gustav Zigeuner W.-Bernd Lintschinger Alfred Fuchsgruber Krystyna Kollmann 《Monatshefte für Chemie / Chemical Monthly》1976,107(1):155-170
Heating 1-alkyl- or 1-aryldihydro-6-methyl-2(1H)-pyrimidinethiones5, 6 in an inert medium causes rearrangement to 4-alkylamino-(4-arylamino-)-5,6-dihydro-2(1H)-pyridinethiones11, 12, probably via the methylene form29, by thermal heterolysis of the N1/C2 bond and exchange of the alkylamino (arylamino) group 1 through the carbon atom of the methylene group 6. The aminodihydropyridinethiones11, which can be regarded as cyclic derivatives of 3-aminothiocrotonamide, react with bistrichlorophenylmalonate under diacylation, and with formaldehyde and primary amines to yield aminodialkylation products of the enamine system, tetrahydro-4-hydroxy-7,7-dimethyl-5-thioxopyrido[4,3-b]pyridine-2(1H)-ones13, 14 and hexahydro-7,7-dimethylpyrido[4,3-d]pyrimidine-5(6H)-thiones18, 19, 21 respectively. H2O2 converts11 to the corresponding 4-aminodihydro-2(1H)-pyridones22, which can be reconverted into11 with P4S10.11 reacts with alkyl halides to 2-alkylthiodihydropyridines23, 24, 25. The mechanism of the methylpyrimidine-pyridine rearrangement is discussed. 相似文献
58.
Five 2-amino-4-(x-pyridyl)- and 2-amino-4-(x-quinolyl)thiazoles have been synthesized by the condensation of thiourea with bromoacetylpyridines and -quinolines. The reaction of pyridyl pyridylmethyl ketones with thiourea and halogens produced four 2-aminothiazoles possessing pyridyl substituents in 4- and 5-positions on the thiazole ring. Treatment of N-(3-pyridyl)- and N-(3-quinoiyl)thiourea with α-bromoketones gave seven new 2-(3-pyridyl)amino- and 2-(3-quinolyl)aminothiazoles. The ultraviolet spectra of the pyridyl- and quinolyl- substituted 2-aminothiazoles were recorded. 相似文献
59.
FLUORESCENCE QUANTUM YIELDS OF 124-kDa PHYTOCHROME FROM OAT UPON EXCITATION WITHIN DIFFERENT ABSORPTION BANDS 总被引:1,自引:0,他引:1
Claudio G. Colombano Silvia E. Braslavsky Alfred R. Holzwarth Kurt Schaffner 《Photochemistry and photobiology》1990,52(1):19-22
Abstract— A fluorescence quantum yield (emission at650–850 nm) of π= (2.3 ± 0.3)10−3 was measured for the red-absorbing form (Pr) of 124-kDa phytochrome from etiolated oat seedlings ( Avena sativa ) upon excitation in the Soret band at Λexc = 380 nm. The small difference between this value and the previously determined quantum yield with Λexc = 640 nm, π= (3.5 ± 0.4)10−3 is attributed to a blue-absorbing emitter responsible for the "anomalous" or "blue" emission of the chromoprotein in the region from ca. 400 to 550 nm. The absorption of Pr at 380 nm is consequently somewhat lower than that measured directly from the spectrum. Processes from upper excited states of the Pr phytochromobilin-derived chromophore other than rapid relaxation to the emitting state are not important. A quantum yield of Φ ' 1.2 times 10−3 is estimated for the blue fluorescence. The proportion of the blue emitters relative to Pr appears to be relatively high. 相似文献
60.
Alfred Hüller 《Zeitschrift für Physik B Condensed Matter》1980,36(3):215-225
In the last few years tunneling transitions have been observed for the highly symmetric groups CH4, CD4, NH
4
+
, and CH3 rotating in various environments. Typically the tunneling lines shift to lower energies with increasing temperatures. In this paper the shift of the tunneling energy is calculated in a microscopic approach to the problem. The coupling of the rotating groups to the lattice modes is studied in two stages. First the rotating group is coupled to a single oscillator, then to the modes of a Debye crystal. The first calculation leads to a set of discrete tunneling lines with an energy that diminishes as the oscillator is excited into higher levels. The second approach yields a single tunneling line shifted down-wards with increasing phonon population. The shift is proportional toT
4. The calculation explains the energy shift of the tunneling lines with reasonable values for the coupling parameters. In some cases also a broadening has been observed which does not follow from our calculations. 相似文献