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1.
Stacy J. Taylor Robson F. Storey 《Journal of polymer science. Part A, Polymer chemistry》2004,42(23):5942-5953
3,3′,5,5′‐Tetrakis(2‐chloro‐2‐propyl)biphenyl (biphenyl tetracumyl chloride, BPTCC) and 1,3‐bis[3,5‐bis(2‐chloro‐2‐propyl)phenoxy]propane (diphenoxypropane tetracumyl chloride, DPPTCC) were synthesized as initiators for quasiliving cationic polymerization of isobutylene (IB). In the synthesis of BPTCC, tetrafunctionality was achieved via the coupling of dimethyl 5‐bromoisophthalate (DMBI) using nickel dibromide bis(triphenylphosphine) and zinc in the presence of a base; in the synthesis of DPPTCC, two equivalents of dimethyl 5‐hydroxyisophthalate were linked via reaction with 1,3‐dibromopropane in the presence of potassium carbonate. Both initiators were used to initiate the polymerization of IB under quasiliving cationic polymerization conditions. PIB initiated from BPTCC revealed a chain end/molecule value (as determined by 1H‐NMR) of 3.85, verifying the nearly exclusive production of 4‐arm polyisobutylene (PIB). GPC analysis revealed a narrow peak representing the target four‐arm PIB, with a slight shoulder at high elution volumes (low molecular weights). GPC analysis of the PIB initiated by DPPTCC revealed multimodal distributions, suggesting the formation of two‐, three‐, and four‐arm star polymers during the polymerization. This behavior was attributed to Friedel–Crafts alkylation of the initiator core after the addition of one IB unit, which was activated by the electron‐donating oxytrimethyleneoxy linking moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5942–5953, 2004 相似文献
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Single-crystal X-ray analyses have defined the structures and solid-state conformations of (±)-N-benzoyl-3-methylaminocycloheptanone [(±)-]and (+)-N-benzoyl-4-methylaminocycloheptanone [(±)]. Resolution of (±)-[4- methylaminocycloheptanone α 1-hydroxytropane]to yield the (+)-enantiomer. Identical in all respects with the free base from natural (+)-physoperuvine, was achieved via the di-p-toluoyl-(+)-tartrate salt. 相似文献
7.
Reginald B. Little 《Journal of Cluster Science》2003,14(2):135-185
The discovery, synthesis, characterization, and applicability of carbon nanotubes have produced tremendous excitement and interest among scientists and engineers. In particular, the use of these unique tubular nanostructures for new strong lightweight materials, nanoelectronics, fuel storage and cells, electron emitters and bio, scanning probe microscopy, and chemical sensing devices has created an intense effort to advance the synthesis so as to mass produce carbon nanotubes with control over diameter and helicity. The massive and controlled synthesis of this heralded nanostructure has been a great challenge. Although significant progress has advanced the preparation, more synthetic development is required. The syntheses have so far involved three main approaches: arc discharge vaporization, laser vaporization, and catalytic chemical vapor deposition. The synthetic trend has progressed to a point where further advancement with these techniques will require a better understanding of the mechanism of nucleation and growth. The mechanics of carbon nanotube nucleation and growth involve very complex and diverse phenomena occurring under extreme conditions and on the mesoscopic scale. As yet the detail mechanism is unknown. Difficulties with experimental probing and computational simulation have increased the mystery of this mechanism. This review presents an account of research on the synthesis of carbon nanotubes and the mechanism of formation. This overview includes all three mentioned synthetic approaches and hybrids thereof. On the basis of this broad account a comprehensive mechanism for carbon nanotube nucleation and growth naturally arises. This mechanism is qualitative and it hopes to inspire more quantitative exploration and synthetic advancement. 相似文献
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Kimball DB Haley MM Mitchell RH Ward TR Bandyopadhyay S Williams RV Armantrout JR 《The Journal of organic chemistry》2002,67(25):8798-8811
The synthesis and study of dehydrobenzoannulene (DBA)-dimethyldihydropyrene (DDP) hybrids as models for the investigation of aromaticity in weakly diatropic systems is reported. Three new monofused DBA-DDP hybrids have been synthesized, and their NMR spectra are discussed with regard to quantifying the aromaticity remaining in multibenzene-fused DBAs. Nucleus-independent chemical shifts, determined at a series of locations for each compound, bond lengths, and (1)H and (13)C NMR chemical shifts were calculated and used to probe the aromaticity of these hybrids. Systems where more than one annulene/DBA is fused to the DDP core have also been obtained, and their potential use in photoinduced isomerization applications is discussed. 相似文献
9.
James Grimshaw Charles S. Sell Reginald J. Haslett 《Journal of mass spectrometry : JMS》1974,8(1):381-386
The mass spectra of some methoxy and methyl derivatives of 2-methylbenzophenone have been examined. Loss of a substituents from 3′-and 4′-positions as well as the previously known loss from 2′-positions are important fragmentation processes. Thus, these fragmentations are of little use in locating substituents on benzophenones of unknown structure. Deuterium labelling shows the [M - 1]+ ion from 3′,4,4′,5,5′-pentamethoxy-2-methyl benzophenone to be due largely to loss of hydrogen from 2′- and 6′-positions. 相似文献
10.
Birgit Langenbach-Kuttert Ronald Roß Reginald Gruehn 《Monatshefte für Chemie / Chemical Monthly》1985,116(11):1275-1289
Niobiumoxidefluorides Nb59O147F, Nb31O77F, Nb65O161F3 and Nb34O84F2 were prepared by reaction of Nb2O5 and Nb3O7F at 1 270°C. These niobiumoxidefluorides have blockstructures which were examined by high resolution electron microscopy. The observed images of the crystal structures were compared with computer simulated images. 相似文献