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311.
Isamu Onishi Kyung‐Youl Baek Yuzo Kotani Masami Kamigaito Mitsuo Sawamoto 《Journal of polymer science. Part A, Polymer chemistry》2002,40(12):2033-2043
A half‐metallocene iron iodide complex [Fe(Cp)I(CO)2] induced living radical polymerization of methyl acrylate (MA) in conjunction with an iodide initiator [(CH3)2C(CO2Et)I, 1 ] and Al(Oi‐Pr)3 to give polymers of controlled molecular weights and narrow molecular weight distributions (MWDs) (Mw/Mn < 1.2). With the use of chloride and bromide initiators, the MWDs were broader, whereas the molecular weights were similarly controlled. Other acrylates such as n‐butyl acrylate (nBA) and tert‐butyl acrylate (tBA) can be polymerized with 1 /Fe(Cp)I(CO)2 in the presence of Ti(Oi‐Pr)4 and Al(Oi‐Pr)3, respectively, to give living polymers. The 1 /Fe(Cp)I(CO)2 initiating system is applicable for the synthesis of block and random copolymers of acrylates (MA, nBA, and tBA) and styrene of controlled molecular weights and narrow MWDs (Mw/Mn = 1.2–1.3). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2033–2043, 2002 相似文献
312.
313.
ESR study of free radicals formed upon UV irradiation of nitropentafluoroacetone in various solvents
B. L. Tumanskii V. I. D'yachenko Yu. I. Lyakhovetskii N. N. Bubnov S. P. Solodovnikov A. F. Kolomiets 《Russian Chemical Bulletin》1993,42(3):466-468
The formation of CF3C(O)CF2N(O.)O2CF2C(O)CF3 free radicals upon the UV irradiation of nitropentafluoroacetone (1) in toluene and mesitylene is established by ESR. The most likely cause of their formation is the one-electron oxidation of the solvents by photoexcited1 followed by decay of the radical anion formed from1 with the expulsion of an NO2 anion and attachment of the radical to a molecule of original1. The irradiation of 1 in triethylsilane results in the elimination of a fluoride ion and fixation of a CF3COCFN(O–)O' radical. UV irradiation of ketone1 in pentane results in the abstraction of a hydrogen atom from the solvent and the formation of a CF3COCF2N(OH)O ' radical.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 512–514, March, 1993. 相似文献
314.
The mechanism of proton exchange between semiquinone neutral radicals 3,6-di-tert-butyl-2-hydroxyphenoxyl (1), 6-tert-butyl-3-chloro-2-hydroxy-4-triphenylmethylphenoxyl, and hydrochloric acid in toluene solutions has been studied. The rate of proton exchange with hydrochloric acid is less than that with acetic acid owing to the higher thermodynamic stability of the radical cation formed upon semiquinone radical protonation by hydrochloric acid. The formation of radical cations and their dimers has been proven by spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 84–87, January, 1993. 相似文献
315.
Eriko Sato Per B. Zetterlund Bunichiro Yamada 《Journal of polymer science. Part A, Polymer chemistry》2004,42(23):6021-6030
α‐(2‐Methyl‐2‐phenylpropyl)acrylate (RS‐2) was examined as a C? C bond‐cleavage type addition–fragmentation chain transfer (AFCT) agent in the benzene solution polymerizations of styrene (St), ethyl methacrylate (EMA), and cyclohexyl acrylate (CHA) with the objective of achieving efficient macromonomer synthesis by radical polymerization. The AFCT efficiency was evaluated in terms of the decrease in the number‐average molecular weight (Mn) upon the addition of the AFCT agent and the number of unsaturated end groups introduced per chain (f). The AFCT efficiency was rationalized by the consideration of the relative importance of AFCT as an end‐forming event and the competition between ‐fragmentation and crosspropagation as adduct radical reaction pathways. In St and EMA polymerizations at 60 °C, RS‐2 resulted in higher f values and lower Mn values than methyl α‐(2‐methyl‐2‐carbomethoxypropyl)acrylate (MMA‐2), and this suggested the facilitation of ‐fragmentation due to the expulsion of the more stable cumyl radical from the RS‐2 adduct radical. Higher f values were observed for MMA‐2 than for RS‐2 in CHA polymerization because of unsaturated end group formation by ‐fragmentation of midchain radicals. However, RS‐2 resulted in lower Mn values for poly(CHA) than MMA‐2 because of a smaller contribution of crosspropagation. Retardation in the presence of the AFCT agents was affected by the balance between b‐fragmentation and crosspropagation and by the addition rate of the propagating radical to the AFCT agent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6021–6030, 2004 相似文献
316.
Masayuki Inoue 《Tetrahedron》2003,59(30):5645-5659
Ladder-shaped polyether natural products show diverse biological activities with extreme potency. As the initial phase of detailed SAR studies of bioactive polyethers, we set out to construct structurally simple mimics. This paper details the divergent synthesis of 6-X-7-6 tetracycles (X=7, 8, or 9) starting from a simple 6-membered ether. Key reactions in the synthesis include (i) the direct formation of an O,S-acetal by the coupling of an alcohol with an α-chlorosulfide, (ii) the construction of a 7-membered ring by radical cyclization, and (iii) cyclization to the 7, 8 or 9-membered ring via a ring-closing metathesis reaction. The neutral reaction conditions of our strategy enable the synthesis of a wide variety of substrates. The results of this study can be applied for the rapid construction of artificial polyether compounds with diversified molecular shapes and sizes. 相似文献
317.
The effects of polyelectrolytes on the inhibition and aggregation of calcium oxalate crystallization
The influence of polyelectrolytes with different architecture on spontaneous batch crystallization of calcium oxalate was investigated. A series of acidic acrylate block copolymers were been made, by radical polymerization, with defined molecular weight and structure. Radical polymerization of acrylic acid (AA) was carried out in the presence of α‐thiopolyethylene glycol monomethylether as a chain transfer agent to produce poly(ethylene glycolblockacrylic acid) copolymers. Poly(ethylene glycol) (PEG) block length in the copolymers was controlled by using three different molecular weight chain transfer agents (Mn = 350, 750 and 2000 g/mol). The presence of copolymers inhibited the crystal growth of calcium oxalate possibly through adsorption onto the active growth sites for crystal growth due to the charge and hydrophilic effects. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
318.
Four new derivatives of podophyllotoxin, N'-podophyllic acid-N-[3-(2, 2, 5, 5-te-tramethyl-pyrrolinenyloxy)] semicarbazide(GP-11, 6), podophyllic acid [3-(2,2,5,5-te-tramethyl-pyrrolinenyloxy)]hydrazone (GP-12, 7), podophyllic acid-[4-(2, 2, 6, 6-tetramethyl-1-hydroxy piperidine)]hydrazone(GP-1-OH, 8) and podophyllic acid[4-(2,2, 6, 6-tetramethyl piperidine)]hydrazone(GP-1-H, 9) were synthesized. The inhibition effect of the four new compounds on L-1210 cells were determined. The antitumor activity and toxicity of GP-1(2), GP-1-OH(8), GP-1-H(9) and VP-16-213(1) were discussed. 相似文献
319.
V. A. Dodonov Yu. L. Kuznetsova M. A. Lopatin A. A. Skatova 《Russian Chemical Bulletin》2004,53(10):2209-2214
The polymerization of methyl methacrylate initiated by dicyclohexyl peroxydicarbonate at 30 °C was studied in the presence of tri-n-butylboron and a series of quinones, namely, p-benzoquinone, chloranil, and 2,5-di-tert-butyl-p-benzoquinone, whose concentration changed from 0.25 to 2.00 mol.%. The initial polymerization rate and molecular weight of poly(methyl methacrylate) depend on the structure and concentration of quinone. The growth radicals react with p-benzoquinone and chloranil predominantly at the C=C bond, while they react at the C=O bond of 2,5-di-tert-butyl-p-benzoquinone. The terminal stable oxygen-centered radicals that formed react with alkylborane, terminating reaction chains and generating alkyl radicals into the bulk. The latter are involved in chain initiation.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2114–2119, October, 2004. 相似文献
320.
A novel one-dimensional manganese(Ⅱ) complex containing nitronyl nitroxide radical [Mn2(IM2-py)2(Ac)2((μ1.1-N3)(μ1,3-N3) . EtOH]n was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group p21/n. Each Mn(Ⅱ) ion is six-coordinated in a distorted octahedral environment. The two N atoms of the nitronyl nitroxide radical and the two O atoms of acetate ligands are in the equatorial plane, whereas the two different azido bridging ligands are in trans axial position. Mn(Ⅱ) ions are linked by nitrogen atom of μ1,1-azido and oxygen atoms of two carboxy groups to form a Mn-Mn unit. Mn-Mn units are linked by azido ligands through u1,3 bridging style to form a one-dimensional chain. The compound is connected by the coordination bonds,π-π interactions and hydrogen bonds as a three-dimensional structure. Magnetic susceptibility data support that there are stronger antiferromagnetic interactions between the radical and Mn(Ⅱ) ion, weak antiferromagnetic inter 相似文献