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71.
Masahiko Okada Keigo Aoi Wataru Mizuno Shinji Ito 《Journal of polymer science. Part A, Polymer chemistry》1993,31(5):1135-1140
New polyesters 6a–6c consisting of 2,4-linked tetrahydrofuran rings were synthesized by bulk polycondensation of methyl trans- and cis-4-hydroxytetrahydrofuran-2-carboxylates ( 5a and 5b ) and a stereoisomeric mixture of methyl 4-hydroxy-5-methyltetrahydrofuran-2-carboxylate ( 5c ) at high temperature. These monomers were prepared from methyl glycolate or methyl lactate and diethyl maleate through a four-step reaction sequence. The polycondensation was carried out without solvent at different temperatures ranging from 150 to 220°C. Titanium isopropoxide was most effective among the catalysts examined, giving polyesters with number-average molecular weights up to 2 × 104. Polyester 6a consisting of trans-2,4-linked tetrahydrofuran rings was soluble in trifluoroacetic acid and a mixed solvent of chloroform and methanol (10/1, v/v). Polyester 6b composed of cis-2,4-linked tetrahydrofuran rings was soluble in dimethyl sulfoxide and dimethylformamide in addition to the two solvents for 6a . Polyester 6c with 5-methyl-substituted tetrahydrofuran rings was composed of a mixture of stereoisomeric units and thus was soluble in a variety of solvents including chloroform, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, and dimethylformamide. The glass transition temperatures of 6a, 6b , and 6c determined by DSC were 109, 88, and 66°C. These polyesters were found to be very slowly hydrolyzed in a neutral phosphate buffer solution at ambient temperature. © 1993 John Wiley & Sons, Inc. 相似文献
72.
Masami Kamigaito Kotaro Satoh 《Journal of polymer science. Part A, Polymer chemistry》2006,44(21):6147-6158
The simultaneous control of the molecular weights and the tacticity was attained even during radical polymerization by the judicious combinations of the living/controlled radical polymerizations based on the fast interconversion between the dormant and active species, and the stereospecific radical polymerizations mediated by the added Lewis acids or polar solvents via the coordination to the monomer/polymer terminal substituents. This can be useful for various monomers including not only conjugated monomers, such as acrylamides and methacrylates, but also nonconjugated ones such as vinyl acetate and N‐vinylpyrrolidone. Stereoblock polymers were easily obtained by the addition of the Lewis acids or by change of the solvents during the living radical polymerizations. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6147–6158, 2006 相似文献
73.
Masahiko Imai Lu Gong Xu Kazuo Ametani Mituaki Tutiya 《Journal of polymer science. Part A, Polymer chemistry》1989,27(5):1763-1773
Polypropylene films were irradiated with 60Co γ-rays in vacuum or in air and stored in air. Just after irradiation, the concentration of carbonyl group of the sample irradiated in air only increased with dose. The concentrations of both samples increased with storage time. The more the absorbed doses, the higher the increasing rates. The increasing rate of the concentration of carbonyl group during irradiation in air was higher than those during storage in air. Just after irradiation, the tensile strengths and the elongations of the both samples somewhat increased with dose at the doses less than 5 Mrad, but decreased at doses more than 13 Mrad. The tensile strength and the elongation of the sample irradiated in air decreased with storage time. Those of the sample irradiated in vacuum also decreased with storage time but the decreasing rates were much smaller than those in the sample irradiated in air. The gel fractions of the samples irradiated in vacuum and annealed in vacuum were somewhat higher than those irradiated in vacuum and not annealed. To elucidate high oxidation rate in the sample irradiated in air during and after irradiation, reaction mechanisms were discussed. To clarify the difference of mechanical properties between the samples irradiated in vacuum and in air, the effect of crosslink was considered, together with the oxidation. 相似文献
74.
Shokyoku Kanaoka Masahiko Minoda Mitsuo Sawamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1990,28(5):1127-1136
Amphiphilic block polymers of vinyl ethers (VEs). $\rlap{--} [{\rm CH}_{\rm 2} {\rm CH}\left( {{\rm OCH}_{\rm 2} {\rm CH}_{\rm 2} {\rm NH}_{\rm 2} } \right)\rlap{--} ]_m \rlap{--} [{\rm CH}_{\rm 2} {\rm CH}\left( {{\rm OR}} \right)\rlap{--} ]_n \left( {{\rm R: }n{\rm - C}_{{\rm 16}} {\rm H}_{{\rm 33}} ,{\rm }n{\rm - C}_{\rm 4} {\rm H}_{\rm 9} ;m \simeq 40,{\rm n} = 1 - 10} \right)$ were prepared, each of which consists of a hydrophilic segment with pendant primary amino groups and a hydrophobic poly(alkyl VE) segment. Their precursors were obtained by the HI/I2-initiated sequential living cationic polymerization of an alkyl VE and a VE with a phthalimide pendant (CH2 = CHOCH2CH2Im; Im; phthalimide group), where the segment molecular weights and compositions (m/n ratio) could be controlled by regulating the feed ratio of two monomers and the concentration of hydrogen iodide. Hydrazinolysis of the imide functions gave the target polymers which were readily soluble in water under neutral conditions at room temperature. These amphiphilic block polymers lowered the surface tension of their aqueous solutions (0.1 wt%, 25°C) to a minimum ? 30 dyn/cm when the hydrophobic pendant R was n-C4H9 (n = 4–9). The polymers with n-C4H9 pendants in the hydrophobic segment exhibited a higher surface activity than those with n-C16 H33 pendants. The surface activity of the polymers also depended on the pH of the polymer solutions; the surface activity increased in more basic solutions where the ionization of the amino group (? NH2)2? NH3⊕) is suppressed. 相似文献
75.
Masahiko Takahashi Tomoko Gunji Akiko Ichikawa 《Journal of heterocyclic chemistry》2002,39(5):1029-1033
Reactions of 1,2‐dihydro‐4H‐3,1‐benzothiazine‐2,4‐dithiones (trithioisatoic anhydrides) 3 with N‐substi‐tuted benzylamines 9 gave 1,2‐dihydroquinazoline‐4‐thiones 10 , o‐thioureidodithiobenzoic acid 11 , o‐aminothiobenzamides 12 , 2‐amino‐3,1‐benzothiazine‐4‐thiones 13 , or quinazoline‐2,4‐dithiones 14 , depending on the kinds of amine and the reaction solvent. On the other hand, reaction of 3 with trialkyl phosphites afforded dialkyl (1,2‐dihydro‐2‐thioxo‐4H‐3,1‐benzothiazin‐4‐yl)phosphonates 18 . 相似文献
76.
Tanaka T Murakami K Kanda A Patra D Yamamoto S Satoh N Kim SW Rahman SM Ohno H Iwata C 《The Journal of organic chemistry》2001,66(21):7107-7112
A total synthesis of (+/-)-stemodinone, a tetracyclic stemodane diterpene, from the known tricyclic methyl olefin 11 is described. The key steps involve an efficient ring-exchange reaction and palladium(0)-catalyzed lactone migration. The ring-exchange strategy for controlling the stereochemistry was based on an initial Diels-Alder reaction to form a new ring followed by cleavage of the original ring. Cleavage of the original ring of the Diels-Alder adduct 9 was achieved by an initial regio- and chemoselective Baeyer-Villiger oxidation followed by the Pd(0)-catalyzed lactone-migration reaction reported by us. 相似文献
77.
We have investigated the aggregation phenomena in a polydisperse colloidal dispersion composed of ferromagnetic particles by means of the cluster-moving Monte Carlo method. The results have been compared with those for a monodisperse system. The internal structures of aggregates have been analyzed in terms of the radial distribution function in order to clarify the quantitative differences in the internal structures of clusters. In addition, the cluster size distribution and angular distribution function have been investigated. The results obtained in the present study are summarized as follows. In a monodisperse system, open necklacelike clusters are formed and they extend with increasing strength of the magnetic particle-particle interaction. In a polydisperse system with a small standard deviation in the particle size distribution, sigma=0.2, larger necklacelike clusters are formed and some looplike clusters can also be observed. In a polydisperse system with a larger standard deviation, sigma=0.35, clumplike clusters are formed for a weak magnetic particle-particle interaction. For a stronger magnetic interaction, larger size clusters that exhibit a complicated network structure are formed. These complicated cluster formations found in a polydisperse system are mainly due to the effect of the presence of larger particles. 相似文献
78.
Yoshihisa Kurasawa Waka Satoh Izumi Matsuzaki Yuka Maesaki Yoshihisa Okamoto Ho Sik Kim 《Journal of heterocyclic chemistry》2003,40(5):837-843
The reaction of the quinoxaline N‐oxides 7a,b with diethyl ethoxymethylenemalonate gave the 1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 8a,b , whose reaction with N‐bromosuccinimide or N‐chlorosuccinimide afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 9a‐d. The reaction of compounds 9a‐d with hydrazine hydrate resulted in hydrolysis and decarboxylation to provide the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 10a‐d , whose reaction with nitrous acid effected oxidation to furnish the 3‐halogeno‐4‐hydroxy‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 11a‐d , respectively. The reaction of compounds 11a‐d with hydrazine hydrate afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4‐ols 12a‐d , whose oxidation provided the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4(1H)‐ones 6a‐d , respectively. Compounds 6a‐d had antifungal activities in vitro. 相似文献
79.
Fukuzumi S Yuasa J Satoh N Suenobu T 《Journal of the American Chemical Society》2004,126(24):7585-7594
Photoinduced electron transfer from a variety of electron donors including alkylbenzenes to the singlet excited state of acridine and pyrene is accelerated significantly by the presence of scandium triflate [Sc(OTf)(3)] in acetonitrile, whereas no photoinduced electron transfer from alkylbenzenes to the singlet excited state of acridine or pyrene takes place in the absence of Sc(OTf)(3). The rate constants of the Sc(OTf)(3)-promoted photoinduced electron-transfer reactions (k(et)) of acridine to afford the complex between acridine radical anion and Sc(OTf)(3) remain constant under the conditions such that all the acridine molecules form the complex with Sc(OTf)(3). In contrast to the case of acridine, the k(et) value of the Sc(OTf)(3)-promoted photoinduced electron transfer of pyrene increases with an increase in concentration of Sc(OTf)(3) to exhibit first-order dependence on [Sc(OTf)(3)] at low concentrations, changing to second-order dependence at high concentrations. The first-order and second-order dependence of k(et) on [Sc(OTf)(3)] is ascribed to the 1:1 and 1:2 complexes formation between pyrene radical anion and Sc(OTf)(3). The positive shifts of the one-electron redox potentials for the couple between the singlet excited state and the ground-state radical anion of acridine and pyrene in the presence of Sc(OTf)(3) as compared to those in the absence of Sc(OTf)(3) have been determined by adapting the free energy relationship for the photoinduced electron-transfer reactions. The Sc(OTf)(3)-promoted photoinduced electron transfer from hexamethylbenzene to the singlet excited state of acridine or pyrene leads to efficient oxygenation of hexamethylbenzene to produce pentamethylbenzyl alcohol which is further oxygenated under prolonged photoirradiation of an O(2)-saturated acetonitrile solution of hexamethylbenzene in the presence of acridine or pyrene which acts as a photocatalyst together with Sc(OTf)(3). The photocatalytic oxygenation mechanism has been proposed based on the studies on the quantum yields, the fluorescence quenching, and direct detection of the reaction intermediates by ESR and laser flash photolysis. 相似文献
80.
1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of cyclic ketones and chloromethyl p-tolyl sulfoxide in good yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium at −78°C to room temperature gave spirocyclic enaminonitriles in high yields. Acidic treatment of the enaminonitriles afforded spiro[4.n]alkenones in good yields. By using an unsymmetrical cyclic ketone, α-tetralone, and optically active chloromethyl p-tolyl sulfoxide, this procedure afforded enantiomerically pure spiro[4.5]decenone in good yield with excellent asymmetric induction from the sulfoxide chiral center. By using this method a formal total synthesis of a racemic spirocyclic sesquiterpene, acorone, was realized. 相似文献