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81.
Nowadays, about 150 natural products comprising an allenic or cumulenic structure are known. The chemistry of these compounds has turned out to be a very attractive and prolific area of interest: advances in the isolation and characterization of new allenic natural products have led to the establishment of efficient synthetic procedures which in many cases also open up an access to enantiomerically pure target molecules. Inspired by the intriguing biological activities of many allenic natural products, allene moieties are now systematically introduced in pharmacologically active classes of compounds (steroids, prostaglandins, amino acids, nucleosides). The functionalized allenes thus obtained often exhibit impressive activities as mechanism-based enzyme inhibitors, cytotoxic, or antiviral agents. A prerequisite for further developments in this field is the efficient stereoselective synthesis of allene derivatives. 相似文献
82.
Synthesis of phthalide derivatives using nickel-catalyzed cyclization of o-haloesters with aldehydes
Rayabarapu DK Chang HT Cheng CH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):2991-2996
The reaction of o-bromobenzoate (1 b) with benzaldehyde (2 a) in the presence of [NiBr(2)(dppe)] (dppe=1,2-bis(diphenylphosphino)ethane) and zinc powder in THF (24 hours, reflux temperature), afforded 3-phenyl-3H-isobenzofuran-1-one (3 a) in an 86 % yield. Similarly, o-iodobenzoate reacts with 2 a to give 3 a, but in a lower yield (50 %). A series of substituted aromatic and aliphatic aldehydes (2 b, 4-MeC(6)H(4)CHO; 2 c, 4-MeOC(6)H(4)CHO; 2 d, 3-MeOC(6)H(4)CHO; 2 e, 2-MeOC(6)H(4)CHO; 2 f, 4-CNC(6)H(4)CHO; 2 g, 4-(Me)(3)CC(6)H(4)CHO; 2 h, 4-C(6)H(5)C(6)H(4)CHO; 2 i, 4-ClC(6)H(4)CHO; 2 j, 4-CF(3)C(6)H(4)CHO; 2 k, CH(3)(CH(2))(5)CHO; 2 l, CH(3)(CH(2))(2)CHO) also underwent cyclization with o-bromobenzoate (1 b) producing the corresponding phthalide derivatives in moderate to excellent yields and with high chemoselectivity. Like 1 b, methyl 2-bromo-4,5-dimethoxybenzoate (1 c) reacts with tolualdehyde (2 b) to give the corresponding substituted phthalide 3 m in a 71 % yield. The methodology can be further applied to the synthesis of six-membered lactones. The reaction of methyl 2-(2-bromophenyl)acetate (1 d) with benzaldehyde under similar reaction conditions afforded six-membered lactone 3 o in a 68 % yield. A possible catalytic mechanism for this cyclization is also proposed. 相似文献
83.
Ga^3+的新萃取体系的界面特性和胶团化作用研究 总被引:1,自引:0,他引:1
研究了Ga~(3+)协萃体系(Ga~(3+)-D_2EHPA-H_2MPA-正十二烷-H_2SO_4)的界面吸附和胶团形成热力学,发现该萃取体系中[H_2MPA]影响D_2EHPA和H_2MPA的界面吸附性质。在中、高[H_2MPA]范围内D_2EHPA与H_2MPA的界面吸附行为相反,D_2EHPA的存在也影响H_2MPA的界面吸附行为。研究了界面张力与各因素关系的数学模型,并获得某些胶团形成和界面吸附特性的物化参数。 相似文献
84.
A copolymer of poly(acrylonitrile-co-styrene) (SAN) was synthesized via an emulsion polymerization method. Novel polymer electrolyte membranes cast from the blends of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), SAN and fumed silica (SiO2) are microporous and can be used in polymer lithium-ion batteries. The membrane shows excellent characteristics such as high ionic conductivity and good mechanical strength when the mass ratio between SAN and PVDF-HFP and SiO2 is 3.5/31.5/5. The ionic conductivity of the membrane soaked in a liquid electrolyte of 1 mol/L LiPF6/EC/DMC/DEC is 4.9×10-3 S cm-1 at 25℃. The membrane is electrochemical stable up to 5.5 V versus Li /Li in the liquid electrolyte. The influences of SiO2 content on the porosity and mechanical strength of the membranes were studied. Polymer lithium-ion batteries based on the membranes were assembled and their performances were also studied. 相似文献
85.
86.
Monodisperse poly(methyl methacrylate) (PMMA) particles containing various concentrations of stearyl methacrylate (SMA) were prepared, and a liquid crystal (LC) was swollen into the particles using a solute co-diffusion method (SCM). Phase separation behaviors between the polymer and LC were monitored by utilizing an optical and a polarized microscope (OM/POM). The monodisperse LC microcapsules were then applied to a polymer-dispersed liquid crystal (PDLC), and the electro-optical properties were investigated. As a result, the threshold and driving voltages were improved when the SMA content increased. The long alkyl chains of SMA in the capsules should exist at the interface of the LC and polymer resulting in an enhancement of phase separation between the polymer and LC, which largely influences the electro-optical properties of PDLC. 相似文献
87.
88.
89.
A need for an elaboration of the methods for synthesis and characterization of activated carbons with a requisite porous structure has existed for a long time. One of the methods giving possibility for creating controlled mesopore and micropore structures deals with the steam gasification of various carbon materials. In this work the effects of calcium catalyst on the catalytic steam gasification of active carbons from plum stones and porous polymers are presented. Determination of micropores capacity and specific adsorption in mesopores have been performed by means of the
s
method, but adsorption on the heterogeneous solids was described by the integral equation with various local isotherms. This equation has been solved by the regularization method. Based on this method the changes in structural parameters of active carbons depending on the amount of calcium catalyst were estimated.Nomenclature
d
width of slit-like micropore
-
F(x)
distribution function of the half-width
-
p
vapor pressure of sorbate
-
p/p
N
relative pressure
- PSAC
Plum Stone Active Carbon
-
average pore radius, nm
-
S
1
relative limit of the validity of experimental point on the adsorption isotherm in the computations by means of regularization method
- SAC
Synthetic Active Carbon
-
S
BET
specific surface area calculated by means of BET method, m2/g
-
S
mes
mesopore surface area, m2/g
-
S
mic
micropore surface area, m2/g
-
T
absolute temperature, K
-
V
mes
sorption capacity of mesopores, cm3/g
-
V
mic
sorption capacity of micropores, cm3/g
-
V
p
sorption capacity of pores, cm3/g
- w/w
weight in weight concentration
-
x
half-width of slit-like micropore, nm
-
x
1
maximum of half-width of micropore slit, nm
-
average half-width of slit-like micropore, nm
-
X
min-X
max
integration limits of thex
Greek Letters Greek Letters
variance of average half-width of slit-like micropore, nm2
-
local relative filling of micropores
-
total relative filling of micropores 相似文献
90.
Ring‐rearrangement metathesis (RRM) refers to the combination of several metathesis transformations into a domino process, in which an endocyclic double bond of a cycloolefin reacts with an exocyclic alkene. RRM has proven to be a powerful method for the rapid construction of complex structures. The extension of the basic ring‐opening–ring‐closing metathesis process by further metathesis steps as well as an examination of the driving forces, limits, scope, recent advantages, and future perspectives of these domino sequences is presented with various examples, thus reflecting the high efficiency and utility of RRM in organic synthesis. 相似文献