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81.
Hans Bürger 《Angewandte Chemie (International ed. in English)》1973,12(6):474-486
In contrast to carbon, silicon fails to form multiple bonds that are stable at room temperature. Consequently molecules in which silicon exhibits coordination numbers (CN) of 1, 2, and 3 may only be obtained at very high or low temperatures. Under these conditions their structural features, including multiple bonds, resemble those of carbon. On the other hand, silicon is capable of forming various hexacoordinated compounds making use of its d orbitals. Nitrogen and oxygen bonded to silicon develop an unusual stereochemistry: planar nitrogen, nearly or completely linear oxygen, and considerable shortening of SiN, SiO, and SiF bonds are specific examples. N(SiR3)2 and CH2SiR3 ligands permit stabilization of unusually low CNs of many metals and give rise to amino and alkyl derivatives of unexpectedly high stability due to the particular electronic, the R3Si group. 相似文献
82.
Hans. R. Kricheldorf William E. Hull 《Journal of polymer science. Part A, Polymer chemistry》1978,16(3):583-595
The tripeptides Phe-Gly-Gly, β-Ala-Gly-Gly, and ?-Aca-Gly-Gly as well as the peptide derivatives δ-isothiocyanatovaleroyl-Gly-Gly and ?-isothiocyanatocaproyl-Gly-Gly were synthesized by using known methods so that the peptide nitrogen between the two glycyl residues was isotopically enriched in 15N to a level of 0.8–0.9%. These monomer units were then used to produce the sequence polymers (Phe-Gly-Gly)n, (β-Ala-Gly-Gly)n, (δ-Ava-Gly-Gly)n, and (?-Aca-Gly-Gly)n. The 18.24 MHz 15N-NMR spectra of the oligo- and polypeptides were obtained by using trifluoroacetic acid as solvent, since the solutions have relatively low viscosity and exhibit a strong negative nuclear Overhauser enhancement of the 15N signals. For comparison, 15N-NMR spectra of the homopolymers (Gly)n, (β-Ala)n, (γ-Abu)n, (δ-Ava)n, and (?-Aca)n were also recorded. The 15N signals from the ω-aminoacyl residues in the sequence polymers appear up to 11 ppm upfield of the signals observed for the homopolyamides. The 15N signals from the two glycyl residues are separated by 3–7 ppm. Comparison with the 13C-NMR spectra of the same polymers indicates that 15N-NMR is better suited for the characterization and sequence analysis of these types of polymers. 相似文献
83.
Hydroxylamine-O-sulfonic acid: a convenient reagent for the conversion of aldehydes into nitriles . Hydroxylamine-O-sulfonic acid (HAS) proved to be an excellent reagent for the conversion of aliphatic, aromatic and heteroatomic aldehydes into nitriles. There, aldehydes in the form of suspension in HAS water solution, react rapidely to give the corresponding nitriles in high yield. Only with formylpyridines could the intermediate oxime-O-sulfonic acids be isolated. 相似文献
84.
Urs P. Wild Hans J. Griesser Vo Dinh Tuan Jean F.M. Oth 《Chemical physics letters》1976,41(3):450-455
The emission spectra of the second excited singlet state of [18] annulene and of monofluoro [18] annulene (in a 3-methylpentane glass at 4 K) are reported. The large energy gap between the first and second excited singlet states inhibits fast internal conversion and favours the appearance of S2 → S0 emission. In addition, fluorescence from the S1 state can be observed in monofluoro [13] annulene by exciting into the S2 or directly into the S1 absorption. 相似文献
85.
86.
Hans Zimmer Adel Amer Douglas Ho R. Palmer-Sungail 《Journal of heterocyclic chemistry》1991,28(6):1501-1510
The reaction pathway of 4-aroyl-3-hydroxy-2(5H)-furanones 1 with diamines depends on the nature of the amine as well as on the applied reaction conditions. Thus, the reaction of 1a-d with 5,6-diamino-1,3-dimethyluracil 5 led to the formation of two isomeric Schiff bases 7a-d and 8a-d . Conversely type 1 compounds reacted with 4,5-diaminopyrimidine 9 or 2,3-diaminopyridine 10 to form the mono acid-base adducts 11a and 11b respectively. When type 1 compounds were reacted with aliphatic diamines 13a-d or p-phenylenediamine and p-xylenediamine, respectively also an immediate formation of acid-base adducts 15a-f was observed. The reaction of a number of O-methylated type 1 compounds with 1,2-ethylenediamine afforded the novel seven-membered ring compounds 18a-d in good yields. The analogous reaction of O-alkylated 1a with o-phenylenediamine 2 or 2,3-diaminonaphthalene gave the expected tricyclic ring systems 19 or 20 . 相似文献
87.
In the crystalline N,N′-dimethylated uracil derivatives 2a , b , the kinetically stabilized enol group forms an H-bond with O? C(4), as demonstrated by increased shielding of specifically labelled 2a and 2b in the 17O-NMR spectra (Δδ(17O)(C(4)—O) ? ?30 ppm); absence of dilution and solvent effects show that the H-bridge is intra-molecular, forming an eight-membered chelate ring. The (apparent) shielding effect Δδ(17O) in 2a, b is larger than that in salicylamide. The strong H-bond explains why the enols 2 , in spite of the absence of steric hindrance, are kinetically stabilized. 相似文献
88.
On treatment with HSO3F in SO2C1F at 0°, 3-hydroxy-2,2-dimethyl-3-phenyl-propionic acid ( 1a ) is transformed into 2-phenyl-3-methyl-2-butenoic acid ( 2a ) (isolated yield: 40–44%). Using monolabelled [3-13C]- 1a ( 1a *) and doubly labelled [1,3-13C2]- 1a ( 1a **), the migration of HOOC (or a mechanistically equivalent group) was proved; a cross experiment established the intramolecular character of the rearrangement. By following the reaction at low temperature in an NMR. spectrometer, the formation of intermediates and side products was demonstrated. 相似文献
89.
Zusammenfassung Die Pastenmethode gestattet als einziger Zellstreckungstest fördernde und hemmende Wirkungen von außen zugeführter Stoffe am normal gesteuerten pflanzlichen Streckungswachstum gleichzeitig und gleichwertig festzustellen und zu messen. Ihre Beziehung zu anderen Testmethoden wird diskutiert.Auf Grund einer einfachen Überlegung über die allgemeinen Wirkungsmöglichkeiten von Wirkstoffen innerhalb der von ihnen beeinflußten Systeme wird eine allemeine Wirkstoffhypothese entwickelt, welche annimmt, daß ein Wirkstoff entweder eine Wirkgruppe und eine Affinität zu einer Wirklücke oder eine Hemmgruppe und eine Affinität zu einer Hemmlücke oder aber beides haben muß, wenn er Wirkstoffeigenschaften besitzen soll. Die im speziellen Fall als Gruppen oder Affinitäten bezeichneten Strukturbereiche können sich auch überschneiden oder untereinander identisch sein, doch ist ihre anfänglich getrennte Betrachtung aus heuristischen Grüden in jedem Falle zweckmäßig. Beliebige Stoffe können jeweils eine oder mehrere der genannten Gruppen oder Affinitäten in verschiedenen Stärken aufweisen und sich im Wirkstoffsystem dementsprechend verhalten. Es wird eine Deutung verschiedener Konzentrations-Wirkungskurven auf Grund dieser Hypothese gegeben.Die Kennzahlen der Konzentrations-Wirkungskurven von über 50 verschiedenen Stoffen im Pastentest werden mitgeteilt und vergleichend diskutiert.Mit 5 Abbildungen.Die hier veröffentlichte Wirkstoffhypothese wurde zusammen mit einem Teil des Materials dieser Mitteilung am 13. 8. 1953 beim Wuchsstoff-symposium der Universität Lund/Schweden erstmals vorgetragen. 相似文献
90.