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191.
192.
4-Diazo-1,2,3-triazoles thermolyze and photolyze to 4-1,2,3-triazolylidenes which (1) convert benzenes to 4-phenyl-1,2,3-triazoles or/and (2) isomerize to α-diazonitriles which react carbenically with benzenes by addition, ring-expansion or substitution processes. 相似文献
193.
Vijaykumar D Mao W Kirschbaum KS Katzenellenbogen JA 《The Journal of organic chemistry》2002,67(14):4904-4910
Two different synthetic routes were explored for the synthesis of fluoro furanyl norprogesterone (FFNP) 1, a high-affinity ligand for the progesterone receptor (PgR) that is being developed as a PET imaging agent for PgR-positive breast cancer. Both approaches proceed through a key intermediate, triol 5. The first approach, starting from keto-ketal 2, employed a dioxenyl group as a synthon for installing a corticosteroid side chain in keto-alcohol 4. The second approach, starting from propargylic acetate 12b, involved the application of a two-step method, a Pd(II)-catalyzed oxidative rearrangement followed by a base-catalyzed acetate rearrangement of the intermediate unsaturated acetate 13b, to generate the requisite corticosteroid side chain in keto-acetate 14b. This intermediate was further elaborated to the final product 1 via efficient dihydroxylation with potassium permangnate, furan acetalization with scandium triflate, and mesylation and fluorination reactions. The palladium-catalyzed route is considerably more efficient than the dioxene approach for the synthesis of key intermediate triol 5, and the scandium triflate-catalyzed acetalization, in particular, led to a considerable improvement in the overall yield of the endo furan acetal alcohol 16a. This route provides a major improvement in the overall yield of the final progestin target, FFNP 1. 相似文献
194.
The γ-substituted β-diketonate 2,4-dioxo-3-pentyl 4-[4-(n-octyloxy)cinnamoyl]oxybenzoate 1 and its pyrazole and isoxazole derivatives (2 and 3 respectively) have been synthesized and characterized by the spectroscopic methods and elemental analysis. The mesogenic properties of these compounds have been studied by polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). A monotropic nematic mesophase was observed for the β-diketonate 1, in contrast, the pyrazole 2 displays an enantiotropic smectic A and isoxazole 3 exhibits an enantiotropic nematic mesophase. The relationship between the structure and liquid crystalline properties has also been discussed. 相似文献
195.
JIN Xiang-qun ZHANG Jing-min XU Hui ZHOU Yan WANG Guang-shu ZHAO Yan-qiu ZHANG Han-qi 《高等学校化学研究》2006,22(2):185-188
Introduction Malignantdiseasesarecharacterizedbytheunreg ulatedgrowthoftransformedcells.Inrecentyears,dramaticinsightsintothemolecularmechanismsofthis phenomenonhavebeenachievedfrombasiccancerre search.Manycellularfunctionsareregulatedbychan gesingeneexpr… 相似文献
196.
Chi Chen Chang‐Wei Su Chun‐Wei Yeh Hui‐Ling Hu Jhy‐Der Chen Ju‐Chun Wang 《中国化学会会志》2006,53(2):299-303
The reaction of N,N′‐di(2‐pyridyl)formamidine (HDpyF) with MnCl2‐4H2O afforded the complex MnCl2(HDpyF), which was characterized by X‐ray crystallography. The HDpyF ligand chelates to the Mn(II) center through the first and the third nitrogen atoms to form a six‐membered ring, leaving the second and the fourth nitrogen atoms uncoordinated. The HDpyF ligand is crystallographically disordered such that two different molecules can be solved. The neutral HDpyF ligand adopts the new s‐cis‐syn‐s‐trans conformation. 相似文献
197.
Lei He Hui‐Min Liu Xiao‐Lan Luo Wen‐Qin Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(2):o104-o106
The title compound, 2‐{N‐[2‐(2‐hydroxybenzamido)ethylammonioethyl]aminocarbonyl}phenolate, C18H21N3O4, crystallizes in a zwitterionic form as a result of intermolecular proton transfer and possesses a negatively charged phenolate group and a protonated amino group. The 2‐hydroxybenzamide and 2‐(aminocarbonyl)phenolate moieties attached to the two ends of the C—C—N—C—C backbone adopt a cis conformation in relation to this backbone. All N‐ and O‐bound H atoms are involved in hydrogen‐bond formation; the zwitterions are first linked into head‐to‐tail dimers, which are further organized into a two‐dimensional network parallel to the crystallographic bc plane. 相似文献
198.
Asapowerfulandversatileone-electrontransferreductant,Sml,hasbeenappliedwidelyinorganicsynthesis'.OurpreviousworksonthereductionofnitrocompoundsandreductivecleavageofS-S,Se-Se,Te-TebondswithSml,'ledustoinvestigatethesimultaneousreductionofnitrogroupandS-SbondbySml,.Benzothiazolinesderivativesareimportantreagentsandusefulintermediatesinorganicsynthesisandpharmaceuticalchemistry.Forinstance,theycanbeusedasadditionagentsforphotographicemulsions",effectiveacaricides",antituberculousagents",lubr… 相似文献
199.
一个新的噻二唑衍生物H2ADTZ与锰的二维聚合物的合成与晶体结构(英) 总被引:2,自引:0,他引:2
A new 1,3,4 thiadiazole-derivative ligand 2,5-(s-acetic acid) dimercapto-1,3,4 thiadiazole (H2ADTZ) and its one-dimensional manganese polymer Mn(ADTZ)·4H2O had been synthesized and structurally characterized by X-ray single crystal diffraction in this paper. The Mn(Ⅱ) ion is coordinated with a distorted octahedron by two oxygen atoms from neighboring two deprotonated ligands ADTZ2- and other four oxygen atoms from four coordinated water molecules. The structural feature of the title compound is the formation of one-dimensional manganese chains polymer through the bridging of dioxygen O-O units. In the solid state structure of the complex, one-dimensional manganese chains are joined together by the weak intermolecular hydrogen bonds and vander Waals interactions forming a two-dimensional supramolecular compound. Furthermore, the UV spectra and electro-chemical properties of the title compound were also investigated. CCDC: 260532. 相似文献
200.
Anomalous room-temperature specific heats have been seen experimentally by Knapp and coworkers in highT
c
superconductors. The measurements depart from 3N k
B
+
0
T by an amount of order
0
T. We present a theory for this, based on the fact that electronphonon interactions cause both electron band energies
k
n
and phonon frequencies
Q
µ
to be weakly temperature-dependent. First an observation is made which we call Brook's Theorem: the shiftE
k
n
(Q
µ) of the electron energy
k
n
due to adding one phonon in modeQ
µ, is identical to the shift
Q
µ
(k
n) of the phonon energy
Qµ due to adding one electron in the statek
n. Second, we assert that to sufficient accuracy whenT>
D
, entropy of the system of interacting electrons and phonons equals the entropy which would be calculated for non-interacting particles, except that theT-dependent energiesE
kn
(T) and
Q
µ
(T) should be used. A proof to orderu
2 (whereu is phonon displacement amplitude) was given in the thesis of one of us. Third, we use Brook's Theorem to show that the corrections C
el and C
ph to the specific heat due toT-dependence of electron and phonon energies respectively, are identically equal and have order of magnitude
0
T. All these results are valid in adiabatic approximation to orderu
2, and fail at low temperatures where non-adiabatic corrections are large. 相似文献