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1.
2.
The anion-assisted shift of trans-cis isomerization equilibrium of a palladium(II) complex containing acetanilide functionalities brought about by allosteric hydrogen bonding interactions has been established by UV/Vis, 1H NMR, 31P NMR and ESI-MS studies.  相似文献   
3.
A total synthesis of cyclothialidine ( 1 ), a new DNA gyrase inhibitor isolated from Streptomyces filipinensis, is described. The synthetic concept was tested by preparing the lactone 13 (Scheme 2) which contains the characteristic bicyclic core entity of 1 . Key features of the synthesis of 1 are: preparation of 3,5-dihydroxy-2,6-dimethylbenzoic acid ( 23 ) from 3,5-dihydroxybenzoic acid ( 19 ) by two consecutive Mannich aminomethylation/hydrogenation sequences; benzylic N-bromosuccinimide bromination of an ester derivative 25 thereof and its subsequent coupling with Boc-Ser-Cys-OMe ( 11 ); cyclization of the ω-hydroxy acid 29 29 to the 12-membered lactone 30 using preferably Mitsunobu conditions; completion of the peptidic side chains of 1 using Boc strategy (Scheme 4). Optically pure cis-N-(tert-butoxycarbonyl)-3-hydroxy-L -proline ((–)- 14 ) was obtained by resolution of the racemate via an efficient reaction sequence containing a lipase-catalyzed enantiospecific acetate hydrolysis (Scheme 3). The structure of natural 1 was confirmed by comparison with the synthetic material. The synthetic route described provides also easy access to analogues of 1 , e.g., via the intermediate 30 .  相似文献   
4.
4,4-Dimethyl-2-phenyl-2-thiazolin-5-thione (4) reacts with 2,3-diphenylcyclopropenone (2a) at 145°C and with benzonitrilio-2-propanide (6) at room temperature to yield the 1,6-dithia-spiro[4.4]nonadienes 5 and 7, respectively.  相似文献   
5.
Nanocomposites containing pure or organically modified nanoboehmites of different sizes were prepared by melt compounding with polypropylene. The samples were UV light irradiated in artificial accelerated conditions representative of solar irradiation (λ > 300 nm) at 60 °C in air. The chemical modifications resulting from photooxidation were followed by IR and UV-visible spectroscopies. The presence of pristine nanoboehmites was shown to change the rate of oxidation of polypropylene by reducing the oxidation induction period due to the presence of residual processing antioxidant. The differences of the oxidation induction periods between the nanocomposites and the pristine polymer disappear after solvent extraction of the antioxidant. The inefficiency of traditional antioxidant in retarding the photooxidation of polypropylene containing nanodispersed boehmite is proved. Antioxidant migration to the boehmite surface induced by the preferential interaction with the polar filler is proposed as an explanation. The oxidative behaviour of the organically modified boehmites was shown to depend on the type of organic substituent. p-Toluenesulfonate reduces the adsorption of antioxidants while the presence of a long-chain alkyl benzensulfonate increased the oxidation rate by generation of radical initiators.  相似文献   
6.
The intercalation of some amines (aniline, benzylamine, cyclohexylamine,piperidine, pyridine, pyrazine and piperazine) into -titaniumphosphate, Ti(HPO4)H2O,has been investigated by the batch method and/or by exposing the host to thevapour of the amines. The changes in the interlayer distance of the solidduring the intercalation process was followed by X-ray powder diffraction.The new intercalates were characterised by chemical and thermal analysis.Materials with a monolaminar and/or bilaminar arrangement of amine moleculesin the phosphate interlayer region are obtained depending on the nature ofthe amine. Due to steric hindrance, saturated phases are not obtained forall amines studied. The thermal decomposition of the intercalates (nitrogenatmosphere), takes place in three stages: dehydration, removal of amines andcondensation of the hydrogenphosphate to pyrophosphate groups.  相似文献   
7.
A set of derivatives of cyclopentaneacetic acid cis-substituted at position 3 by nucleoside bases (both purines and pyrimidines) were prepared and characterized (see 11, 14 , and 23a, b; Schemes 2–4). These molecules are carbocyclic analogs of 2′,3′-dideoxy-5′-homonucleosides. In this synthesis, the skeleton was constructed from norbornanone and a novel method based on Mitsunobu chemistry used for the introduction of nucleoside-base substituents. The scope of this method was further explored via the preparation of a cyclobutyl analog of dideoxyguanosine (see 17 , Scheme 3).  相似文献   
8.
Title compound 1 was synthesized by a published route which had to be modified (seven steps from readily obtainable starting materials). Characterization of 1 was achieved by spectroscopic means (FAB-MS, 1H-NMR, including 2D-COSY). Furthermore, commercially available reference material purchased for comparison, was unequivocally established to be 10 , i.e. incompletely deprotected 1 .  相似文献   
9.
The thermal degradation of a highly chlorinated paraffin, (Cl 70% w/w)(CP), used as a fire retardant additive for polymers, has been studied by TG, DTA and TVA. The main volatile degradation product is HCl which is eliminated in two steps. To 60–70% dehydrochlorination an apparent zero order reaction occurs with a detectable rate from 250°C, probably initiated at labile chlorine atoms. The apparent activation energy of the process is 40 kcal/mole. A charred residue containing 35% chlorine is obtained. This residue undergoes nearly complete dehydrochlorination in the range 300–600°C.  相似文献   
10.
In esterifications of secondary alcohols catalyzed by immobilized lipase B from Candida antarctica (Novozym 435) the E-values decreased during the reaction. Hydrolysis of the corresponding butanoates showed the opposite effect. When an enantiopure (R)-alcohol, related but different, was added to the transesterification reaction, the E-value was significantly enhanced.  相似文献   
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