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141.
den Brok MW Nuijen B Miranda E Floriano P Munt S Manzanares I Beijnen JH 《Journal of chromatography. A》2003,1020(2):251-258
ES-285 x HCl [(2S,3R)-2-amino-3-octadecanol hydrochloride] is a novel investigational anticancer agent, which has shown in vitro and in vivo cytotoxic activity against various tumor cell lines with selectivity for certain solid tumors. The pharmaceutical development of ES-285 x HCl warranted the availability of an assay for the quantification and purity determination of ES-285 x HCl active pharmaceutical ingredient (API) and its pharmaceutical dosage form. A liquid chromatographic method (LC) comprising of derivatisation of ES-285 x HCl with phenylisothiocyanate and UV-detection was developed. The method was found to be linear, precise and accurate. The assay also proved selectivity as determined by analysing ES-285 x HCl in combination with 15 analogues and in combination with hydroxypropyl-beta-cyclodextrin, the excipient used in the lyophilised pharmaceutical dosage form. Stress testing showed that the degradation products were separated from the parent compound, confirming its stability indicating capacity. The method was found robust as determined with design of experiments (DoE), which made it possible to predict system suitability responses in worst case experimental conditions and to define criteria for system suitability testing. 相似文献
142.
Different transformations of chiral epoxy esters 1 afford two different amino gamma-butyrolactones 2 and 6, and amino gamma-butenolides 8, by different nucleophilic opening-closing processes. [reaction: see text] 相似文献
143.
Sánchez-Moreno MJ Gómez-Coca RB Fernández-Botello A Ochocki J Kotynski A Griesser R Sigel H 《Organic & biomolecular chemistry》2003,1(10):1819-1826
The synthesis of (1H-benzimidazol-2-yl-methyl)phosphonic acid, H2(Bimp)+/-, is described: 2-chloromethylbenzimidazole was reacted with ethylchloroformate to give 1-carboethoxy-2-chloromethylbenzimidazole which was treated with trimethyl phosphite and after hydrolysis with aqueous HBr H2(Bimp)+/- was obtained. In H2(Bimp)+/- one proton is at the N-3 site and the other at the phosphonate group; both acidity constants were determined in aqueous solution by potentiometric pH titrations (25 degrees C; I = 0.1 M, NaNO3) and this furnished the pKa values of 5.37 +/- 0.02 and 7.41 +/- 0.02, respectively. The acidity constant for the release of the primary proton from the P(O)(OH)2 group of H3(Bimp)+ was estimated: pKa = 1.5 +/- 0.2. Moreover, Bimp2- can be further deprotonated at its neutral (N-1/N-3)H site to give the benzimidazolate residue, but this reaction occurs only in strongly alkaline solution (KOH); application of the H_ scale developed by G. Yagil (J. Phys. Chem., 1967, 71, 1034) together with UV spectrophotometric measurements gave pKa = 14.65 +/- 0.12. Comparisons with acidity constants taken from the literature show that this latter pKa value is far too large and this allows the conclusion that an intramolecular hydrogen bond is formed between the (N-1/N-3)H site and the phosphonate group of Bimp2-; the formation degree of this hydrogen-bonded isomer is estimated to be 98 +/- 2%. The general relevance of this and the other results are shortly discussed and the species distribution for the Bimp system in dependence on pH is provided. 相似文献
144.
García-Granados A López PE Melguizo E Moliz JN Parra A Simeó Y Dobado JA 《The Journal of organic chemistry》2003,68(12):4833-4844
Several triterpenic derivatives, with the A-ring functionalized, were semisynthesized from oleanolic and maslinic acids. The reactivities of sulfites, sulfate, and epoxides in these triterpene compounds were investigated under different reaction conditions. Moreover, contracted A-ring triterpenes (five-membered rings) were obtained, by different treatments of the sulfate 7. From the epoxide 8, deoxygenated and halohydrin derivatives were semisynthesized with several nucleophiles. Ozonolysis and Beckmann reactions were used to yield 4-aza compounds, from five-membered ring olanediene triterpenes. The X-ray structure of sulfate 7 is given and compared with density functional theory geometries. Theoretical (13)C and (1)H chemical shifts (gauge-invariant atomic orbital method at the B3LYP/6-31G*//B3LYP/6-31G* level) and (3)J(H,H) coupling constants were calculated for compounds 5-9 and 34-36, identifying the (R)- or (S)-sulfur and alpha- or beta-epoxide configurations together with 4-aza or 3-aza structures. 相似文献
145.
Íñigo X. García-Zubiri Gustavo González-Gaitano Miguel Sánchez Josér; Ramón Isasi 《Journal of inclusion phenomena and macrocyclic chemistry》2004,49(3-4):291-302
The inclusion complexes of β-cyclodextrin (β-CD) with naphthalene and some of its derivatives in the solid state have been studied by infrared spectroscopy. Digital subtraction, deconvolution and curve fitting have been used to investigate the interactions between the naphthalene derivatives andβ-CD. Several preparation methods for the solid dispersions have been tested, using FTIR as an effective tool to evaluate the interactions at the molecular level. The effects of temperature and humidity on the spectra have been also analyzed. A carbonyl moiety in the guest molecule can increase the stability of the complex by establishing specific interactions with the hydroxyl groups of the CD cavity rims. The stability of the complexes is higher for 2-naphthylacetate than that for 1-naphthyl acetate, andso is the degree of association of its carbonyl groups. On the other hand, 2-acetylnaphthaleneforms very stable inclusioncomplexes although its carbonyl groups appear to be significantly less associated. 相似文献
146.
Summary A polarimetric study of the tungsten (VI)-gluconic acid system in an excess of metal reveals the formation of four stable complexes: two monomers with 1 : 2 and 2: 1 stoichiometries and two dimers of 2:2 composition. The pH ranges of these species, the amount of acid equivalents their formation requires, and their conditional stability constants have also been calculated.The probable coordination of the organic ligand to the metallic centre in solutions containing different metal : ligand ratios has been investigated by13C-n.m.r. spectroscopy. The results confirm the formation of different complexes depending on the reagent which is in excess. The behaviour of the system when the metal is in excess is related to that of other polyhydroxylic ligands such as mannitol and sorbitol. 相似文献
147.
Teresa M V D Pinho e Melo Cláudia S J Lopes António M d'A Rocha Gonsalves Ana M Beja José A Paix?o Manuela R Silva Luiz Alte da Veiga 《The Journal of organic chemistry》2002,67(1):66-71
Nucleophilic substitution reactions of 2-halo-2H-azirines 1a, 1b, 1d, and 1e with potassium phthalimide and aniline allowed the preparation of new substituted 2H-azirines 2-5. The reactions of 2-bromo-2H-azirine 1a with methylamine led to the synthesis of alpha-diimines 7 and 8. 2-Halo-2H-azirines were also established as building blocks for the synthesis of a range of heterocyclic compounds, namely, quinoxalines 10a-10d, 3-oxazoline 14, and 2H-[1,4]oxazines 18 and 20. X-ray crystal structures of alpha-diimine 7, 3-oxazoline 14, and 2H-[1,4]oxazine 18 are reported. 相似文献
148.
Roybal JE Pfenning AP Storey JM Gonzales SA Turnipseed SB 《Journal of AOAC International》2003,86(5):930-934
A simple liquid chromatographic (LC) method is presented for the determination of diminazene (DZ) in raw bovine milk. DZ is extracted from raw milk by chilled aqueous centrifugation and is isolated from milk components on a cyano solid-phase extraction column. DZ is eluted by using a methanol-ion pairing reagent. A Phenomenex LUNA CN column and an acetonitrile-buffered mobile phase with a counter ion are used for gradient LC. The LC effluent is monitored at a detection wavelength of 372 nm by using a deuterium lamp. Under the parameters described, the retention time of DZ is 8-10 min with a peak area response of 6.5 mAU/ng. The method demonstrated excellent precision over all levels tested (25-400 ppb) with an overall average recovery of 90.4 +/- 14.5%. The method is applicable to the monitoring of milk for DZ residues at the 25 ppb level with a limit of quantitation of 10 ppb. 相似文献
149.
The tautomeric properties of isoguanine (also named 2-oxoadenine or 2-hydroxyadenine) have been studied in the gas phase, in different pure solvents, and in the DNA environment using state of the art theoretical methods. Our results show that isoguanine constitutes an unique example of how tautomerism can be modulated by the environment. Compared to the tautomeric preference in the gas phase, both polar solvents and the DNA microenvironment dramatically change the intrinsic tautomeric properties of isoguanine. Tautomers which are important in physiological conditions are less than 1/10(5) of the total population of isoguanine in the gas phase. The impact of the present findings in the understanding of spontaneous mutations and in the design of new nucleobases with multiple recognition properties is discussed. 相似文献
150.
Martínez AG Vilar ET Barcina JO De La Moya Cerero S 《Journal of the American Chemical Society》2002,124(23):6676-6685
The effect of a bridgehead methyl group on the hydride ion affinity in the gas phase of bicyclo[1.1.1]pent-1-yl (1+), 1-norbornyl (3+), cubyl (5+), 1-adamantyl (7+), bicyclo[2.2.2]oct-1-yl (9+),and bicyclo[3.1.1]hept-1-yl (11+) cations has been studied using density functional theory and ab initio methods. It is concluded that the methyl group always increases the stability of the substituted cations. The effect of the solvent on the stability of methyl-substituted cations in relation to the unsubstituted cations has been studied using the polarizable continuum model of the self-consistent reaction field theory. In the case of rearranging cations, the nucleophilic assistance of the solvent is determined by means of the interaction energy of the corresponding water complexes. It is concluded that the solvent causes the relative stabilization of the parent cations. As a consequence, most of the methyl-substituted bridgehead derivatives show a lower solvolysis rate than the corresponding unsubstituted compounds. A nonqualitative explanation of the methyl effect on the relative stability of bridgehead cations in both gas phase and solution is given for the first time. The ratios of solvolysis products in the case of rearranging bridgehead cations have also been computed from the relative stability of the intermediate water complexes. 相似文献