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91.
Zusammenfassung Es werden einstufige Synthesen desGlomerins (2) [1,2-Dimethyl-4(1H)-chinazolinon] und desArborins (3) [1-Methyl-2-benzyl-4(1H)-chinazolinon] bekanntgegeben.
Syntheses of heterocycles, CXXX: Glomerine and arborine
A one step synthesis ofglomerine (2) [1.2-dimethyl-4(1H)-quinazolinone] andarborine (3) [1-methyl-2-benzyl-4(1H)-quinazolinone] is described.相似文献
92.
The oxidation of aldehydes by dicyclohexyl-18-crown-6-potassium permangante complex is presented. Results obtained by this procedure showed that the presence of crown ether (DCC) and the catalyst play an important role in the oxidation of the aldehydes. The stoichiometry found corresponds to 2 μeq of permanganate per 1 μmol of aldehydes in all cases. Alcohols and ketones are not oxidized. Finally, a method for quantitative evaluation of aldehydes is proposed. 相似文献
93.
Mahlert C Sieber SA Grünewald J Marahiel MA 《Journal of the American Chemical Society》2005,127(26):9571-9580
Streptogramin B antibiotics are cyclic peptide natural products produced by Streptomyces species.In combination with the synergistic group A component, they are "last line of defense" antimicrobial agents against multiresistant cocci. The racemization sensitivity of the phenylglycine (Phg(7)) ester is a complex challenge in total chemical synthesis of streptogramin B molecules. To provide fast and easy access to novel streptogramin antibiotics, we introduce a novel chemoenzymatic strategy in which diversity is generated by standard solid phase protocols and stereoselectivity by subsequent enzymatic cyclization. For this approach, we cloned, overproduced, and biochemically characterized the recombinant thioesterase domain SnbDE TE of the pristinamycin I nonribosomal peptide synthetase from Streptomyces pristinaespiralis. SnbDE TE catalyzes regioselective ring closure of linear peptide thioester analogues of pristinamycin I as well as stereoselective cyclization out of complex in situ racemizing substrate mixtures, enabling synthesis of Streptogramin B variants via a dynamic kinetic resolution assay. A remarkable substrate tolerance was detected for the enzymatic cyclization including all the seven positions of the peptide backbone. Interestingly, SnbDE TE was observed to be the first cyclase from a macrolactone forming NRPS which is additionally able to catalyze macrolactamization of peptide thioester substrates. An N-methylated peptide bond between positions 4 and 5 is mandatory for a high substrate turnover. The presented strategy is potent to screen for analogues with improved activity and guides our understanding of structure--activity relationships in the important class of streptogramin antibiotics. 相似文献
94.
The ion product of water and the dissociation constants of carbonic acid have been determined in 0.1, 1.0, 3.0, and 5.0M NaClO4 at 25°C. The ion product of water K
w
'
has been evaluated by emf measurements with a combined glass electrode in NaClO4 solutions containing 0.001–0.1M HCLO4 or NaOH. The product K
H
'
K
l
'
K
2
'
of the Henry constant for CO2 and the dissociation constants for H2CO3 have been determined by titration of carbonate solutions equilibrated with pCO2 =10–3.52 atm, and K
2
'
has been evaluated by potentiometric titration and by measuring the H+ concentration at fixed HCO
3
–
and CO
3
2-
concentrations. The ion interaction (Pitzer) equations are applied to describe the constants K
w
'
, K
2
'
and K
H
'
H
1
'
K
2
'
as a function of the NaClO4 concentration. The experimental data are used to evaluate the mixing parameters
i/ClO
4 and
i/ClO
4
-/Na+ fori = OH
-,HCO
3
-
andCO
3
2- 相似文献
95.
Stephan D. Stamatov 《Tetrahedron letters》2006,47(15):2543-2547
Glycidyl esters and ethers undergo a regioselective and stereospecific opening of the oxirane ring upon treatment in chloroform in the presence of pyridine with trimethylsilyl halide (TMSX, X = Cl, Br, or I) and a mixture of carboxylic acid (CA)-trifluoroacetic anhydride (TFAA), to produce the corresponding C2-O-acylated vicinal halohydrins in high yields. 相似文献
96.
Stephan?HaiberEmail author Xingtao?Ai Henning?Bubert Moritz?Heintze Volker?Brüser Waltraut?Brandl Gabriela?Marginean 《Analytical and bioanalytical chemistry》2003,375(7):875-883
Plasma chemically modified carbon nanofibers were characterized by X-ray photoelectron spectroscopy with regard to the content of carbon, oxygen, and nitrogen and the contribution of carboxylic groups or ester, carbonyl and hydroxylic groups or ether on the surface. Unfortunately, X-ray photoelectron spectroscopy only provides an average value of the first 10 to 15 molecular layers. For comparison, depth profiles were measured and wet chemical methods were applied to estimate the thickness of the functionalized layer and the distribution of oxygen-containing functional groups within the near-surface layers. The results indicate that the fiber surface is covered by a monomolecular oxygen-containing layer and that plasma treatment allows a complete oxygen functionalization of the uppermost surface layer. The best conditions for plasma treatment found within the set of parameters applied to generate complete functionalization are: plasma gas O(2)/Ar ratio 1:1, gas pressure 1-1.5 hPa, plasma power 80 W, treatment time >or= 5 min. Additionally, three quick and easy methods are presented to estimate the efficiency of plasma treatment with regard to surface functionalization: pyrolysis, contact angle measurements, and light permeability measurements of aqueous carbon nanofiber suspensions. 相似文献
97.
Synthesis and derivatization of daptomycin: a chemoenzymatic route to acidic lipopeptide antibiotics
Grünewald J Sieber SA Mahlert C Linne U Marahiel MA 《Journal of the American Chemical Society》2004,126(51):17025-17031
Daptomycin is a branched cyclic nonribosomally assembled acidic lipopeptide, which is the first clinically approved antibiotic of this class. Here we show that the recombinant cyclization domain of the Streptomyces coelicolor calcium-dependent antibiotic (CDA) nonribosomal peptide synthetase (NRPS) is a versatile tool for the chemoenzymatic generation of daptomycin derivatives. Linear CDA undecapeptide thioesters with single exchanges at six daptomycin-specific residues were successfully cyclized by CDA cyclase. Simultaneous incorporation of all six of these residues into the peptide backbone and elongation of the N-terminus of CDA by two residues yielded a daptomycin derivative that lacked only the beta-methyl group of l-3-methylglutamate. Bioactivity studies with several substrate analogues revealed a significant role of nonproteinogenic constituents for antibacterial potency. In accordance with acidic lipopeptides, the bioactivity of the chemoenzymatic assembled daptomycin analogue is dependent on the concentration of calcium ions. Single deletions of the four acidic residues in the peptide backbone suggest that only two aspartic acid residues are essential for antimicrobial potency. These two residues are strictly conserved among other nonribosomal acidic lipopeptides and the EF-motif of ribosomally assembled calmodulin. Based on these findings CDA cyclase is a versatile catalyst that can be used to generate novel daptomycin derivatives that are otherwise difficult to obtain by chemical modification of the parental tridecapeptide to improve further its therapeutic activity. 相似文献
98.
Zusammenfassung Die Abhängigkeit der Struktur des o-Hydroxymandelsäurelactons von Lösungsmittel und Temperatur wird mit Hilfe IR- und NMR-spektroskopischer Methoden nachgewiesen.
The temperature and solvent dependence of the structures of 2-hydroxymandelic acid lactone and dioxindole have been shown by IR and NMR spectroscopy.相似文献
99.
Metal Complexes with Anionic Ligands of Elements of the Main Group IV. VIII Pentacarbonyltrihalogenostannidometalate(O) Complexes of Chromium, Molybdenum, and Tungsten with Fluorine and Iodine Containing Trihalogenostannido Ligands In methylenechloride [As(C6H5)4][SnF3] readily reacts with the metalhexacarbonyls forming the arsoniumsalts of the pentacarbonyltrifluorostannidometalate(O) complexes, [M(CO)5SnF3]? (M ? Cr, Mo, W). Exclusively by the reaction of the intermediately formed complex Cr(CO)5THF only one pure triiodostannidometalate(O) Complex, [N(C2H5)4][Cr(CO)5SnJ3], could be isolated. The trihalogenostannidometalate(O) complexes [M(CO)5SnClX2]? (X ? F: M ? Cr, Mo, W; X ? J: M ? Cr) could be prepared by SnX2-insertion reactions of the [M(CO)5Cl]? complexes. The bonding properties of the halogenostannide ions are discussed on the bases of the IR spectra of their metalate(O) complexes. 相似文献
100.
The protonation and deprotonation rates of the coordinated amide group in the Cu2+ complexes with Nα-(2-pyridyl-methyl)-glycinamide (I) and Nα-(2-pyridyl-methyl)-glycineethylamide (II) have been studied by stopped flow techniques. It is shown that the rate determining step of the formation of the complex with the deprotonated amide group is given by the rate of water dissociation from Cu2+. Weaker bases than OH? or stronger acids than water can react by a different path, in which the proton transfer and/or the rotation from the O-co-ordinated into the N-co-ordinated form and vice versa is rate determining. 相似文献