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41.
The synthesis of 2′,6′-diazafolic acid was accomplished by the condensation of 2-acetylamino-4(3H)pteridinone-6-earboxaldehyde (XIV) with diethyl N-[(5-amino-2-pyrimidinyl)carbonyl]-L-glutamate (XIII) followed by reduction of the anil double bond and alkaline hydrolylic cleavage of the N2-acetyl and ethyl ester protecting groups. Intermediate XIII was prepared by starling with 5-nitro-2-styrylpyrimidine (VI) and proceeding via 5-arnino-2-styrylpyrimidine (IX). The henzyloxycarbonyl derivative of IX was prepared and oxidized to the corresponding 5-benzyloxycarbonylaminopyrimidine-2-carboxylic acid (XI). The coupling of XI with diethyl L-glutamate followed by hydrogenolysis of the henzyloxycarbonyl function afforded the desired intermediate XIII. 2′,6′-Diazafolic acid was a potent inhibitor of Streptococcus faecium and displayed marginal activity against leukemia 1,1210 in mice. 相似文献
42.
[reaction: see text]. Polyethylene glycol (PEG)-bound poly-L-leucine acts as a THF-soluble catalyst for the Juliá-Colonna asymmetric epoxidation of enones. Excellent enantioselectivities may be obtained even with short chain length polyleucine. FT-IR investigations have determined that the catalytically active polyleucine components of these copolymers have an alpha-helical structure. 相似文献
43.
In a study of redox reactions on columns, the work of Cerrai and Testa has been extended. It has been shown that insolubility of the redox compound is the most important factor and that adsorptive forces play little or no part. A useful redox column method for the determination of iron and vanadium, which compares favourably with that using a Jones reductor column, has been developed. The redox potentials of several substituted hydroquinones have been measured. 相似文献
44.
Turner DR Henry M Wilkinson C McIntyre GJ Mason SA Goeta AE Steed JW 《Journal of the American Chemical Society》2005,127(31):11063-11074
Four isomorphous complexes of formula [M(L)(4)(H(2)O)(2)]SO(4).2H(2)O (M = Co, 1a; Ni, 1b; Cu, 1c; Zn, 1d) have been isolated and characterized by single-crystal X-ray diffraction and neutron diffraction using the quasi-Laue diffractometer VIVALDI at the Institut Laue-Langevin as well as by thermogravimetric analysis. The structures contain a discrete, strongly hydrogen-bonded water tetramer which causes a significant distortion of the metal coordination sphere in each case. Partial atomic charges and hardness analysis (PACHA) calculations reveal that the shortest hydrogen bonds are not the strongest in this constrained, cyclic solid-state structure and show that the distortion at the metal center is caused by the drive to maintain the integrity of the water tetramer. The system undergoes a disorder-order transition on slow cooling that provides insight into the nature of communication between water squares. 相似文献
45.
R.M.G. Roberts 《Tetrahedron》1980,36(22):3281-3287
The rates of reaction of Tl (III) tris(trifluoroacetate) with benzene toluene and t-butylbenzene in solvent trifluoroacetic acid have been measured by an NMR method. The reaction products have been unambiguously determined from the thallium-hydrogen coupling constants. In the case of toluene, p-tolylthallium bis(trifluoroacetate) crystallised from reaction mixtures.Thalliation was shown to be reversible and to be between one and two orders of magnitude slower than mercuriation. The inductive order of the reactivity (tBu > Me ? H) was found in contrast to the hyperconjugative order for mercuriation. Hammett plots using σ+ values yielded a ? value of ?7.4 but the limited data correlated better with σ values (? = ?12.8). A primary isotope effect of 5.0 was found for toluene indicating rate-determining proton transfer. The mechanism is discussed in the light of these and other findings. In addition the rates of interconversion of the products of mercuriation of toluene are reported from NMR data. 相似文献
46.
P. John Roberts 《Theoretical chemistry accounts》1969,14(3):184-191
In the limiting case of the free-electron theory where the electron motion is constricted to one dimension, the one-dimensional Coulomb potential gives rise to divergent interaction integrals. It is shown that a proposal by Olszewski to remove the divergenses by first evaluating the integrals in the three-dimensional case and then passing to the limit of one dimension only is incorrect, and that convergent integrals may only be obtained by suitably modifying the original one-dimensional Coulomb potential between particles.
Zusammenfassung In dem Grenzfall des Modells der Freien Elektronen, in dem die Elektronenbewegung auf eine Dimension eingeschrÄnkt ist, ergibt das eindimensionale Coulombpotential divergente Wechselwirkungsintegrale. Es wird gezeigt, da\ ein Vorschlag von Olszewski zur Aufhebung der Divergenz durch übergang von dreidimensionalen zum eindimensionalen Integral falsch ist. Konvergente Integrale können nur durch geeignete VerÄnderung des ursprünglichen eindimensionalen Coulombpotentials erhalten werden.
Résumé Dans le cas limite de la théorie de l'électron libre à une dimension, le potentiel coulombien donne lieu à des intégrales d'interaction divergentes. On montre que la proposition d'Oszewski pour éliminer les divergences, en évaluant d'abord les intégrales tridimensionnelles et en passant à la limite à une dimension, est incorrecte et que des intégrales convergentes ne peuvent Être obtenues qu'en modifiant le potentiel coulombien unidimensionnel entre particules.相似文献
47.
Treatment of dimethyl ketene with ethoxyacetylene 1a, 1-ethoxyoct-1-yne 1b, and 1-ethoxytetrade-1-yne 1c afforded the 3-ethoxycyclobutenones 2a–c. Hydrolysis of 2a–c with dilute hydrochloric acid gave the cyclobutane-1,3-diones 3a–c. The 1H NMR spectra of these compounds indicate that in CDCl3 solution 2,2-dimethylcyclobutane-1,3-dione 3a exists as the diketone, whereas the 2,2,4-trialkylcyclobutane-1,3-diones 3b and 3c exist as the monoenols. 相似文献
48.
Fifteen of twenty-four silver(I) carboxylates examined give useful electron impact mass spectra. The compounds vaporize at moderate temperatures, apparently mainly as dimer with traces of higher oligomer in only a few cases. The molecular ion for the dimer is generally weak or absent, with the most abundant silver containing ion being [Ag2(O2CR)]+ in most cases. Metastable defocusing and deuterium labeling experiments on silver acetate have established some of the fragmentation pathways. The reported loss of carbon dioxide from perfluorocarboxylates to give intense peaks for organosilver ions was not observed in this study. Attempts to obtain spectra on the silver salts of organic materials other than carboxylic acids were successful in several cases. Silver trifluoromethanesulfonate, although much less volatile, gives a spectrum and fragmentation very much like the carboxylates, whereas silver trifluoromethanethiolate gives a complex spectrum which suggests tetramer as a major gas phase species. Of three compounds examined which have silver to nitrogen bonding only silver(II) phthalocyanine is sufficiently volatile to give a spectrum without decomposition. The field desorption spectra of the four compounds examined all show the ions AgnXn ? 1 for X=acetate (n=1 ? 6), X=p-chlorobenzoate (n=1 ? 4), X=methanesulfonate (n=1 ? 7) and X=p-toluenesulfonate (n=1 ? 5). 相似文献
49.
The formation constants of charge-transfer complexes of a number of 9- and 9,10-substituted anthracenes with chloranil have been measured by a spectrophotometric method and the corresponding thermodynamic parameters ΔG°c, ΔH°c and ΔS°c evaluated in various solvents. vmax values of the chargetransfer band for chloranil were linearly related to those for tetracyanoethylene (TCNE). Good correlations were also obtained between vmax and the corresponding ionisation potentials Ip of the donor molecules. In addition ΔG°c varied linearly with Ip and from these correlations, values of ΔG°c, etc. for the corresponding TCNE complexes could be calculated. These values are otherwise very difficult to obtain due to the high reactivity of TCNE. 相似文献
50.