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51.
52.
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
53.
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
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57.
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
58.
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
59.
Pentacoordinate complex cations of the general formula [(C6F5)2SbL3]3+ stabilized as solid salts in combination with tetraphenylborate (BPh4), tetrafluorobroate (BF4) anions, where L=DMSO, Ph3AsO, PyO, DMF, α-, β- and γ-picoline have been isolated. The newly formed complexes were characterized by elemental analysis, molar conductance measurements, solid-state IR and and NMR. From these results, a five-fold coordination around antimony was required. 相似文献
60.
Mahrour A. Lacroix M. Nketsa-Tabiri J. Calderon N. Gagnon M. 《Radiation Physics and Chemistry》1998,52(1-6):81-84
This study was undertaken to determine if a combined treatment (marinating in natural plant extracts or vacuum) with irradiation could have a synergetic effect, in order to reduce the dose required for complete elimination of Salmonella on fresh poultry. The effect of these combined treatments on the shelf-life extension was also evaluated. The fresh chicken legs were irradiated at 0, 3 and 5 kGy. The poultry underwent microbial analysis(mesophilic and Salmonella detection). For each treatment, the total microbial count decreased with increase of irradiation dose. The marinating treatment have a synergistic effect with irradiation treatment to reduce the total microbial count and controlling the proliferation during storage at 4°C. Irradiation of fresh chicken pieces with a dose of 3 kGy appears to be able to extend the microbial shelf-life by a factor of 2. When the chicken is marinating and irradiated at 3 kGy or when irradiated at 5 kGy without marinating, the microbial shelf-life is extended by a factor of 7 to 8. No Salmonella was found during all the experiment in the chicken in air and marinated. However, a presence of Salmonella was found in samples irradiated at 5 kGy under vacuum, in unirradiated samples and samples irradiated at 3kGy in air and under vacuum. 相似文献