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21.
Phosphorus-containing polyanhydride-imides were synthesized from N,N-bis(4-carboxyphthalimido)-3,3′-diphenylalkylphosphine oxide, 3,3′-[N,N′-bis(4-carboxyphthalimido)]benzophenone and their mixtures in two steps via the diacetyl derivatives of the bisimide-carboxylic acids. The resulting polymers have reduced viscosities of 0.06–0.14 dl/g and are soluble in polar aprotic solvents such as DMA, DMF and DMSO, and conc. H2SO4 etc. They have good hydrolytic stability for moisture and water. Phosphorus-containing polymers have little heat-resistance and poor flame-retardance. The benefit of incorporating phosphorus in the polymers is small. 相似文献
22.
The reaction of N-aryl-substituted ketenimines with N,N-disubstituted cyanamides or (MeS)2C=N-CN under high pressure afforded 4-(N,N-disubstituted amino) or 4-(MeS)2C=N-substituted quinazoline derivatives, respectively. These products were formed by [4+2] cycloaddition between the aza-diene moieties of the N-arylsubstituted ketenimines and cyano groups. A 4-(unsubstituted amino)quinazoline derivative was synthesized by hydrolysis of the latter product. 相似文献
23.
Y Arano M Yabuki T Yahata K Horiuchi A Yokoyama 《Chemical & pharmaceutical bulletin》1990,38(11):3099-3101
Modification of the chelate ring structure of technetium-99m (99mTc) dithiosemicarbazone (DTS) chelate was carried out in pursuit of a more stable and lipophilic compound. A new DTS chelating molecule, pentane-2,4-dione bis(N-methylthiosemicarbazone) (PETS), with a 5-6-5 membered chelate ring structure, was synthesized and labeled with 99mTc, PETS generated two 99mTc compounds as major products. Both had much higher stability and lipophilicity than a 5-5-5 membered 99mTc DTS compound, as well as great stability in plasma. Both 99mTc-PETS compounds were rapidly extracted by the brain and heart when injected into mice. Thus, the modified chelate ring structure afforded a preferable characteristics to DTS chelate as for the chelating site for technetium radiopharmaceuticals. 相似文献
24.
A variety of diaryl acetylenes were obtained in good yields when lithium hexamethyldisilazide was added to a solution of arylmethyl sulfone, aryl aldehyde, and chlorodiethylphosphate in THF. In this one‐shot process, a number of transformations such as aldol reaction, phosphorylation of aldolate, and double elimination of the resulting β‐substituted sulfone proceeded successively to afford the desired acetylenes. The one‐shot process was accelerated by the substitution of halogen atoms on the phenyl groups, and unsymmetrically substituted diaryl acetylenes were obtained without contamination of the dehalogenated products. Diaryl acetylenes with other substituents such as CF3, ethoxycarbonyl, dimethylamino, TMS‐acetylene groups, as well as pyridinyl and thienyl moieties were also accessible with this method. However, methoxy‐substituted compounds were obtained in moderate yields under the same conditions, but the yields were increased when lithium diisopropylamide was used instead. 相似文献
25.
A new N-unprotected phosphoramidite method called the "proton-block" approach was developed for the chemical synthesis of oligodeoxynucleotides based on the hitherto simplest and rational principle of acid-base reactions. This concept involves protection of the nucleobases of deoxycytidine and deoxyadenosine with "protons" to convert them to unreactive protonated bases during condensation by use of promoters having pK(a) values lower than 2.8. This strategy was applied to the synthesis of d[CpT] and d[ApT] to check the side reactions associated with the base residues. In this "proton-block" method, 5-nitrobenzimidazolium triflate (NBT) was found to be the best promoter, and THF was superior to CH(3)CN as the solvent so that the concomitant detritylation due to the inherent acidity of the promoter could be greatly suppressed. Application of this strategy to the solid-phase synthesis gave d[CpT], d[ApT], d[ApA], d[CpC], and d[GpT] as almost single peaks in HPLC analysis. Similarly, d[ApApApT] and d[CpCpCpT] were successfully synthesized without significant side reactions. Finally, d[CpCpCpCpCpCpT] and d[ApApApApApApT] were obtained as the main products. In the case of a longer oligomer, d[CpApGpTpCpApGpTpCpApGpT], a mixed solvent of CH(3)CN-N-methylpyrrolidone (1:1, v/v) was superior to THF so that the desired oligodeoxynucleotide could be isolated in a satisfactory yield. These results suggest that DNA synthesis can be carried out simply by using the protonated bases at the oligomer level not only without base protection but also without the capping reaction and the posttreatment of branched chains with MeOH-benzimidazolium triflate that previously was requisite. It is concluded that most of the reactions and solvent effects involved in this strategy can be explained in terms of simple acid-base reactions. Some problems associated with the previous posttreatment are also discussed with our own results. 相似文献
26.
Morita A 《Journal of computational chemistry》2002,23(15):1466-1471
The polarizability of a water molecule in liquid is evaluated via ab initio and density functional calculations for water clusters. This work has considerably improved our previous effort [J Chem Phys 1999, 110, 11987] to attain quantitative accuracy for polarizability. The calculations revealed that the water polarizability in the liquid is reduced from that in the gaseous phase by 7-9%. These results suggest significant implications for polarizable water models. 相似文献
27.
A high-performance liquid chromatographic method is described for the selective determination of taurine in biological fluids by post-column fluorescence reaction. Taurine was separated on an adsorption-distribution type Shodex Ionpac KC-811 column. Then it was converted with hypochlorite into the corresponding N-chloramine, which was allowed to react with thiamine to give fluorescent thiochrome. As little as 6 ng per injection of taurine could be determined. The average recoveries of spiked taurine in serum and urine were 99.5 +/- 2.7 and 101.8 +/- 2.9%, respectively. The method could be applied to the assay of taurine in human serum and urine with simple pretreatment. 相似文献
28.
Several 2,4-diaminothiazoles and 2,4-diaminothiophenes could be easily obtained by metallation using LDA from aminomethylthiomethylenecyanamides and aminomethylthiomethylenemalononitrile, respectively. 相似文献
29.
Sano S Takehisa T Ogawa S Yokoyama K Nagao Y 《Chemical & pharmaceutical bulletin》2002,50(9):1300-1302
Tetrasubstituted (Z)-alkenes were readily prepared through the Horner-Wadsworth-Emmons reactions of methyl 2-[bis(2,2,2-trifluoroethyl)phosphono]propionate with aryl alkyl ketones by employing Sn(OSO(2)CF(3))(2) and N-ethylpiperidine. 相似文献
30.
Hirokazu Morisawa Takashi Utagawa Takeshi Miyoshi Fumihiro Yoshinaga Akihiro Yamazaki Koji Mitsugi 《Tetrahedron letters》1980,21(5):479-482
An enzymatic transarabinosylation between 2-chlorohypoxanthine and 1-β--arabinofuranosyluracil gave 9-β--arabinofuranosyl-2-chlorohypoxanthine which was chemically converted to 9-β--arabinofuranosylguanine and its derivatives. 相似文献