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81.
[2.2]Metacyclophane (1) undergoes a variety of reactions according to the reagents and conditions. These include (1) substitution (path a), (2) transannular dehydrogenation (path b and c), (3) cycloisomerization (path d) and (4) transannular hydrogenation. A brief summary of these reactions is presented.The diversity of the reactions of 1 is further explored using benzoyl peroxide (BPO), cupric chloride, aluminum chloride, other metal salts, H2SO4 and FSO3H. With BPO or cupric chloride, one-electron transfer mechanism is postulated. This involves a tautomeric ion pair formed by the intramolecular arylation with an aryl cation radical. A supporting evidence in favor of the mechanism is presented from experiments using various metal salts in different solvents.On the contrary, the reaction with aluminum chloride gives decahydropyrene (8) and octahydropyrene (11) together with cycloisomerization product 5 and dehydrogenation products 2, 3 and 4. When treated with AlCl3HCl 1 gives similar products as above but the product ratios are quite different. The major product is 5 but only a trace amount of 8 is formed. The reaction with H2SO4 or FSO3H also produce 2, 4, 5 and 11. Some mechanistic evidence in favor of the disproportionation reaction is presented. 相似文献
82.
(Styrene-p-chlorostyrene) triblock copolymers of the ABA and BAB types (A—polystyrene; B—poly-p-chlorostyrene) were prepared by anionic polymerization and their conformational behaviours in solutions were studied from measurements of the dipole moments. Two solvents, toluene and cumene, were used for the study; toluene is a good solvent for both polystyrene and poly-p-chlorostyrene whereas cumene is a selective solvent, good for polystyrene but poor for poly-p-chlorostyrene. It was found that the dipole moments of the block copolymers measured in toluene are the same for the ABA and BAB copolymers; in cumene however the dipole moment of the BAB copolymer is smaller than that of the ABA copolymer. The results give an additional support to our previous conclusion that the conformation of the block copolymers in a good solvent such as toluene could be approximated with a pseudo-random coil form; in a selective solvent, however, some anomalies take place in the conformation of the block copolymers, as deduced from intrinsic viscosity, osmotic pressure and light scattering measurements. 相似文献
83.
Sadao Arai Masanori Ishikura Kiyoshi Sato Takamichi Yamagishi 《Journal of heterocyclic chemistry》1995,32(3):1081-1083
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
84.
Mitsuru Ueda Akira Sato Yoshio Imai 《Journal of polymer science. Part A, Polymer chemistry》1979,17(3):783-787
Catalytic actions of various additives were studied in the polycondensation of di(4-nitrophenyl) isophthalate with bis(4-aminophenyl) ether in N-methyl-2-pyrrolidone, and 1-hydroxybenzotriazole (HOBt) was found to be a highly effective catalyst that yielded high-molecular-weight polyamide. In addition to the polycondensation of the 4-nitrophenyl ester, the polymerization of negatively substituted phenyl esters like di(2,4,5-trichlorophenyl) isophthalate was also accelerated by HOBt. For the HOBt-catalyzed aminolysis of esters a bifunctional concerted mechanism that involves an eight-membered transition state was proposed. 相似文献
85.
Tricyclo[3.3.1.1]decanone azine ( adamantanone azine ) reacts with 4-substituted 1,2,4-triazoline-3,5-diones under elimination of diazo adamantane to give a 1,3-dipole ( “azomethinimine” ), which on treatment with dipolahophiles affords the [ 2 + 3] -cycloadducts. The reaction is compared with singlet oxygen oxidation. 相似文献
86.
Mitsuru Ueda Hiroya Sugita Masaki Sato 《Journal of polymer science. Part A, Polymer chemistry》1986,24(5):1019-1026
A convenient method for the synthesis of poly(benzoxazole)s of high molecular weights has been developed. These polymers were prepared readily by direct polycondensation of aromatic dicarboxylic acids containing phenyl either structure with 3,3′-dihydroxybenzidine dihydrochloride using phosphorus pentoxide/methanesulfonic acid (PPMA) as condensing agent and solvent. Polycondensations proceeded fast and was completed within 5 h at 140°C and produced poly(benzoxazole)s with inherent viscosities up to 4.6 dL/g. Model compound work was performed in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(benzoxazole)s showed 10% weight loss in air and nitrogen at 450–505°C and 465–535°C, respectively. 相似文献
87.
Whenp-toluidine is added to an aqueous solution of CTAB, a remarkable increase of viscosity is accompanied by a spectacular elasticity. We detected the existence of extremely elongated rod-like micelles in electron micrographs. SAXS measurements indicate a closely packed array of cylindrical rod-like micelles, brought about when solutions flow through a thin capillary. A scattering maximum ofd=160 Å almost corresponds to the distance between the nearest neighbours of the cylindrical rod-like micelles. This value agrees with the diameter measured on electron micrographs. The second broad peak (d=75 Å) is assigned to a subsidiary maximum of the shape function of the cylinder with infinite length. 相似文献
88.
Synthesis of diphenyl cucurbit[6]uril (CB[6]) has been achieved via co-oligomerization of diphenyl glycoluril and unsubstituted glycoluril. The unsymmetrically substituted CB[6], Ph(2)CB[6], was further converted to a rotaxane incorporating bis(dinitrophenyl)spermine. [reaction: see text] 相似文献
89.
[structure: see text] Absolute stereochemistry of amphidinolides G (1) and H (2), potent cytotoxic 27- and 26-membered macrolides, respectively, isolated from a marine dinoflagellate Amphidinium sp., was determined by X-ray diffraction analysis, synthesis of a degradation product (3) of 2, and interconversion between 1 and 2. 相似文献
90.
Scale-up of wet granulation in a vertical high shear mixer was conducted. Pharmaceutical excipient powders composed of lactose, cornstarch and micro-crystallinecellulose, and hydroxypropylcellulose as a binder were mixed together and then granulated with purified water under various operating conditions and vessel scales. A novel internal stress measurement system was developed and stress of normal and tangential directions that granules received from the agitator blade during the granulation was continuously measured. The results indicated that granules received stress mainly from the tangential direction, which also showed the largest value near at the vessel wall. The effects of the agitator tip speed and the centrifugal acceleration on the measured stress was investigated. It was found that the tip speed of the agitator blade could be the main factor for the granule growth. The physical properties such as strength, size distribution and compressibility of granules prepared by changing the operating conditions and the vessel scales were evaluated and the scale-up characteristics of high shear granulation were investigated experimentally. The results showed that these physical properties had linear correlations with the tip speed. It was finally concluded that the scale-up of high shear granulation could be well conducted by means of the tip speed of the agitator blade. 相似文献