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71.
A. V. Orlinkov T. V. Chulochnikova A. I. Nesmelov V. B. Murachev E. A. Ezhova A. M. Evtushenko 《Russian Chemical Bulletin》1996,45(5):1124-1127
The effects of the nature of halogens in the initiatingtert-butyl halide-aluminum-containing Lewis acid system on the number average molecular weightM
n
and the structure of end groups of polyisobutylene macromolecules obtained in the cationic polymerization of isobutylene in hexane at -78 °C were studied. An increase inM
n
is observed in the transition from chlorine to bromine and iodine, accompanied by a decrease in the fraction of end C=C groups and an increase in the relative content of C-Hal groups (Hal = Cl, Br, and I). When atoms of different halogens are present in the counterion, more bulky atoms preferentially participate in the formation of the end groups. The results are interpreted within the framework of the principle of hard and soft acids and bases.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1184–1187, May, 1996. 相似文献
72.
Hammed H. A. M. Hassan 《Central European Journal of Chemistry》2005,3(4):803-829
A concise method for a stereocontrolled synthesis of a set of selectively protected disaccharides is reported. Coupling of
the donor 11 onto acceptors 23 and 24, promoted by trimethylsilyl triflate-N-iodosuccinimide (TMSOTf-NIS), generated the disaccharides 25 and 26. Under typical conditions, condensation of the fully protected donor 12 onto acceptors 23 and 24 produced the disaccharides 27 and 28. The building blocks 25–28 were prepared in moderate yields having exclusive β-stereoselectivity. A unique pattern of protecting groups distinguished
clearly between positions to be sulfated and functional groups remaining as free hydroxyl groups. Acetyl and/or levulinoyl
esters temporarily protected the positions to be sulfated, while benzyl ethers were used for permanent protection. The anomeric
positions were protected as allyl ethers, whereas the 4′-positions were masked as p-methoxybenzyl (PMB) ethers. The orthogonality of the PMB and allyl groups can then be used for further elongation of the
chain by recurrent deprotection and activation steps. The hydroxyl group, OH-6, of glucosamine moieties was protected as a
TBDPS ether to avoid oxidation. A five-step deprotection/sulfonation sequence was applied to the disaccharide 27 to generate the corresponding sulfated [β-D-GlcUA-2-OSO3Na-(1→4)-β-D-Glc pNAc]-(1→O-Pro) 34. 相似文献
73.
Jo‐Nan Chen Fang‐Ming Hsu Hui‐Chun Wang Chung‐Wen Wu Pao‐Swu Cheng Wen‐Liang Tsai 《中国化学会会志》2006,53(4):931-938
Four series of compounds 11?50 containing terminal alicyclic rings such as cyclohexylmethyl, cyclopentylmethyl, cyclobutylmethyl, and cyclopropylmethyl rings were synthesized and their liquid crystal behavior studied. The ring size and the length of flexible alkoxy chain influence the phase formation in different ways. While the smaller ring and the shorter alkoxy chain tend to favor the formation of the N phase, the larger ring and the longer alkoxy chain tend to favor the formation of the SmC phase. All the compounds except 11 and 21 exhibit SmA phases. The widest temperature range of the N, SmA, and SmC phases are found in the compounds 41 , 46 , and 20 , respectively, which are 75 °C for 41 , 115 °C for 46 , and 100 °C for 20 . 相似文献
74.
Xiao Zhen Liu Fei Wang Dong Dong Luo Xing Guo Guang Qing Lei 《中国化学快报》2007,18(11):1339-1341
The hydroxyl group of carbocyclic nucleosides was inversed when the compounds were treated with Me_3SiCl,KCN and a catalytic amount of NaI in DMF/CH_3CN. 相似文献
75.
徐灿 《高等学校化学学报》1997,18(6):943-946
利用XeCl准分子激光烧蚀多种硅氧多孔结构材料,在负离子通道测得丰富的「(SiO2)nX」^-负离子团簇,并讨论了多孔网结构和表面活性基团的分布对激光能量的吸收,传输及团簇产生的重要作用。 相似文献
76.
Hans-Detlev?GilsingEmail author Jürgen?Angerer Dietrich?Prescher 《Monatshefte für Chemie / Chemical Monthly》2005,136(5):795-801
Summary. The synthesis of an oxidative major metabolite of bis(2-ethylhexyl) phthalate is described. The target molecule and its ring-deuterated isomer were obtained via acylation of the appropriate -hydroxy benzyl ester or the corresponding carboxylate with phthalic anhydride or phthalic anhydride-d4. All transformation steps proceed with high yields. 相似文献
77.
Immobilized sulfhydryl groups were prepared by partial thiolation of NH2-glass beads. The microenvironment of the immobilized SH groups was varied by different chemical modifications of neighboring
NH2 groups. Introduction of a strong charge in the surroundings of immobilized sulfhydryls results in their dramatic stabilization
against autooxidation. This effect is due to the salting of O2 from the surface microlayer of the thiolated beads. 相似文献
78.
We have been studying the problem of heterogeneity of OH groups in zeolites HY for a long time. The heterogeneity was suggested by the shift of the IR band of OH groups restoring upon ammonia desorption and also by the fact that the band of OH groups forming hydrogen bonds was relatively broad (broader than for homogeneous acidic OH). In the present study we present another important argument for heterogeneity: the splitting of the IR band of free OH and OD groups in a zeolite of Si/Al=8.3 dealuminated by (NH4)2SiF6 treatment. Such a splitting is the best seen in low temperature spectra of OD groups. We found less acidic 3640 cm−1 (AlO)(SiO)2SiO1HAl(OSi)3 and more acidic 3625 cm−1 (SiO)3SiO1HAl(OSi)3 groups. The presence of these two kinds of hydroxyls corresponds to the presence of Si(2Al) and Si(1Al), respectively, detected in 29Si MAS NMR spectra. We also found a small amount of strongly acidic 3599 cm−1 hydroxyls interacting with extraframework Al species. 相似文献
79.
Thermal
degradation of vinylidene chloride/[4-(t-butoxycarbonyloxy)phenyl]methyl
acrylate copolymers
B. A. Howell D. A. Spears P. B. Smith 《Journal of Thermal Analysis and Calorimetry》2006,85(1):115-117
Vinylidene chloride polymers containing comonomer
units capable of consuming evolved hydrogen chloride to expose good radical-scavenging
sites might be expected to display greater thermal stability than similar
polymers containing simple alkyl acrylates as comonomer. Incorporation of
a comonomer containing the phenyl t-butyl
carbonate moiety into a vinylidene chloride polymer has the potential to afford
a polymer with pendant groups which might interact with hydrogen chloride
to expose phenolic groups. Copolymers of vinylidene chloride with [4-(t-butoxycarbonyloxy)phenyl]methyl acrylate have been
prepared, characterized, and subjected to thermal degradation. The degradation
has been characterized by thermal and spectroscopic techniques. The degradation
of vinylidene chloride/[4-(t-butoxycarbonyloxy)phenyl]methyl
acrylate copolymers is much more facile than the same process for similar
copolymers containing either [4-(isobutoxycarbonyloxy)phenyl]methyl acrylate
or methyl acrylate, a simple alkyl acrylate, as comonomer. During copolymer
degradation, [4-(t-butoxycarbonyloxy) phenylmethyl
acrylate units are apparently converted to acrylic acid units by extensive
fragmentation of the sidechain. Thus, the phenyl t-butyl
carbonate moiety does function as a labile acid-sensitive pendant group but
its decomposition in this instance leads to the generation of a phenoxybenzyl
carboxylate capable of further fragmentation. 相似文献
80.
Bayó N Jiménez JC Rivas L Nicolás E Albericio F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1096-1103
An optimized solid-phase strategy for the preparation of the cyclic lipononadepsipeptide [N-Mst(L-Ser1), D-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin is reported. The strategy is based on the use of a mild orthogonal protection scheme and the incorporation of the nonproteinogenic amino acid (Z)-Dhb into the peptide chain as the dipeptide Fmoc-Thr(tBu)-(Z)-Dhb-OH. The didehydrodipeptide was synthesized by a water-soluble carbodiimide-induced beta-elimination of a protected dipeptide containing a residue of Thr with its free hydroxy side chain unprotected. 相似文献