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81.
[reaction: see text] An omega-nitro-alpha,beta,psi,omega-unsaturated ester underwent a chemoselective conjugate addition of a nitroolefin moiety with aryllithium to produce a psi-aryl-omega-nitro-alpha,beta-unsaturated ester, which was then stereoselectively cyclized by intramolecular nitro-Michael reaction giving a functionalized cyclohexane applicable to the total synthesis of (+/-)-alpha- and beta-lycoranes.  相似文献   
82.
The first stable silylene-isocyanide complexes, [Tbt(Mes)SiCNAr] (5 c: Ar=Tip, 5 d: Ar=Tbt, 5 e: Ar=Mes*; Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Mes=mesityl, Tip=2,4,6-triisopropylphenyl, Mes*=2,4,6-tri-tert-butylphenyl) were successfully synthesized by the reaction of a kinetically stabilized disilene, [Tbt(Mes)Si=Si(Mes)Tbt] (1), with bulky isocyanides, ArNC (3c-e). The spectroscopic data of 5 c-e and theoretical calculations for a model molecule indicated that 5 c-e are not classical cumulative compounds but the first stable silylene-Lewis base complexes. The reactions of 5 c-e with triethylsilane and 1,3-dienes gave the corresponding silylene adducts, and they underwent isocyanide-exchange reactions in the presence of another isocyanide at room temperature. These results indicate dissociation of complexes 5 c-e to the corresponding silylene 2 and isocyanides 3 c-e under very mild conditions. The reaction of 5 c with methanol gave the MeOH adduct 16, [Tbt(Mes)SiHC(OMe)NTip], which has a hydrogen atom on the silicon atom. This regioselectivity can be explained in terms of the contribution of zwitterionic resonance structures D and E, which have an anion on the silicon atom. This result indicates that 5 c is not a classical cumulene having Si=C double bonds that should react with methanol to give adducts bearing a methoxyl group on the silicon atom. Although the reactions of 5 c-e with electrophilic reagents such as methanol, hydrogen chloride, and methyl iodide gave the formal silylene adducts, the studies on the reaction mechanism by trapping experiments and the observation of the intermediate suggested that the reaction mainly or partially proceeds by initial nucleophilic attack of the silicon atom, as is the case in the formation of 16 in the reaction of 5 c with methanol. It was revealed that 5 c-e show the nucleophilicity of the silicon atom, most likely resulting from the contribution of the zwitterionic resonance structures D and E.  相似文献   
83.
Adsorption properties of activated carbons prepared from waste newspaper by chemical and physical activation were investigated using water vapor, ammonia, methane, and methylene blue (MB) as adsorbents. The water vapor adsorption isotherms show type V behavior and the maximum vapor adsorption of the chemically and physically activated products is about 1050 and 450 ml/g, respectively. The higher water vapor adsorption of the chemically activated products is attributed to the higher specific surface area (S(BET)) and greater hydrophilic activity (arising from the surface oxygen-containing functional groups) than in the physically activated products. The adsorption of ammonia and methane was measured by temperature-programmed desorption (TPD). NH(3) adsorption is found to be higher in the chemically activated product than in the physically activated product while methane adsorption is slightly higher in the physically activated products even though these have lower S(BET) values. In the MB adsorption, the chemically activated products show higher adsorption (390 mg/g) than the physically activated product. These results are suggested to be related to the surface characteristics.  相似文献   
84.
In this preliminary study, a new approach to ion-exclusion chromatography is proposed to overcome the relatively poor conductivity detection response which occurs in ion-exclusion chromatography when acids are added to the eluent in order to improve peak shape. This approach, termed vacancy ion-exclusion chromatography, requires the sample to be used as eluent and a sample of water to be injected onto a weakly acidic cation-exchange column (TSKgel OApak-A). Vacancy peaks for each of the analytes appear at the retention times of these analytes. Highly sensitive conductivity detection is possible and sharp, well-shaped peaks are produced, leading to efficient separations. Retention times were found to be affected by the concentration of the analytes in the eluent, and also by the presence of an organic modifier such as methanol in the eluent. Detection limits for oxalic, formic, acetic, propionic, butyric and valeric acids were 0.1, 0.2, 0.3, 0.3, 0.4 and 0.5 microM, respectively, and linear ranges for some acids extended over two orders of magnitude. Precision values for retention times were 0.21% and for peak areas were <1.90%. The vacancy ion-exclusion chromatography method was found to give detection responses four to 10 times higher than conventional ion-exclusion chromatography using sulfuric acid eluent and two to five times higher than conventional ion-exclusion chromatography using benzoic acid eluent.  相似文献   
85.
A variety of nitrogen‐containing heterocycles were synthesized by passing vapors of aromatic amines over calcium oxide at 450–650 °C under nitrogen carrier gas. Reaction of 2‐aminobiphenyl 3a at 560 °C gave carbazole 4 in 80% yield. Reaction of 2, 2′‐diaminobiphenyl 3b afforded a mixture of carbazole 4 and 4‐aminocarbozole 6b. In the case of 2‐amino‐2′‐nitrobiphenyl 3c, benzo[c]cinnoline 7 was obtained along with carbazole 4. Reaction of 2‐amino‐2′‐methoxybiphenyl 3d gave four products of carbazole 4,4‐hydroxycarbazole 6e, phenanthridine 8 and dibenzofuran 9. Reaction of 2‐aminodiphenylmethane 5a afforded acridine 10. In the case of 2‐aminobenzophenone 5b, acridone 11 was obtained as a major product. Reaction of 2‐aminobenzhydrol 5c gave acridine 10. When 2‐aminodiphenylamine 5d was reacted, phenazine 12 was obtained in good yield. In contrast, reaction of 2‐aminodiphenyl ether 5e produced only 2‐hydroxydiphenylamine 13. Reaction of 4‐aminophenanthrene 14 produced 4H‐benzo[def]carbazole 15 in 61% yield.  相似文献   
86.
The reaction of lithium ester enolate with enones provides a challenge for chemoselectivity, that is, discrimination between a conjugate addition and a 1,2-addition. Asymmetric conjugate addition of a lithium enolate of alpha-trimethylsilanylacetate to acyclic and cyclic alpha,beta-unsaturated ketones was mediated by an external chiral ligand to give the corresponding 1,4-adducts in good enantioselectivity of 74% and good chemoselectivity.  相似文献   
87.
A catalytic asymmetric arylation of sterically tuned imines with arylboroxines was developed by using N-Boc-l-valine-connected amidomonophosphane rhodium(I) catalyst in n-PrOH. The TMS group used for the steric tuning of imines is convertible to other functionalities that are applicable as a key foothold for the carbon-carbon bond-forming coupling reactions.  相似文献   
88.
Influence of the gel size on the morphology, phase diagram, and reflection spectroscopy of the colloidal crystals of thermo-sensitive gel spheres, poly (N-isopropylacrylamide) (pNIPAm), was discussed by adding the data of two gel samples of pNIPAm(400–5) and pNIPAm(600–5) of 412 nm (at 25 °C) and 220 nm (at 45 °C) and of 517 nm (at 20 °C) and 294 nm (at 45 °C), respectively. Colloidal single crystals formed, but not so large compared with the giant crystals of small pNIPAm gels reported previously. The suspensions even with ion-exchange resins were turbid and hard to observe the single crystals clearly with the naked eyes as gel size increased. The critical concentration of melting decreased sharply as the suspensions were deionized with coexistence of the mixtures of cation- and anion-exchange resins. The critical concentration increased as the gel size increased and/or dispersion temperature increased. Density of the gel spheres increased as their size increased. These results demonstrated that the colloidal crystallization takes place by the extended electrical double layers formed around the gel spheres in addition of the excluded volume effect of the gels. Contribution of the electrical double layers on the crystallization increased sharply as temperature increased and gel concentration decreased, respectively. The contribution also increased slightly as sphere size increased, when comparison was made at the same gel concentration in wt.%. The present work clarified that the colloidal interfaces, which are inevitable for the formation of the electrical double layers, are formed between the water phase and gel spheres, though the gel spheres contain a lot of water molecules at the inner sphere region.  相似文献   
89.
Adsorption equilibria at about 1000 atm were measured for aqueous solutions of aromatic compounds. No significant difference between the isotherms at atmospheric pressure and at 1000 atm was found for nitrobenzene and ethylbenzene on activated carbon fiber. The decrease in the amount adsorbed due to the solubility increase with pressure and the increase in the amount adsorbed caused by compression of the adsorbed phase were considered to cancel each other. On the other hand, pressure had a marked effect on the adsorption of L-phenylalanine on a macroreticular adsorbent, resulting in a 1.5 to 2 times larger amount adsorbed at 1500 atm. The pressure effect was greater with larger amounts adsorbed. This implies that the molar volume of the adsorbed state is smaller than those of the pure state and dissolved state, and varies with the amount adsorbed.  相似文献   
90.
The 16c-azonia[6]helicene salts, in which a carbon atom at the inner helix skeleton of [6]helicene is replaced by a quaternary nitrogen atom, have been synthesized by photo-induced intramolecular quater-nization of 2-[2-(1-chloronaphthyl)vinyl]benzo[h]quinolines in acetonitrile.  相似文献   
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