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41.
A variety of 2-azabicyclo[2.1.0]pentanes were synthesized by the intramolecular nucleophilic substitution of cyclopropylmagnesium carbenoids with magnesium anilide. The 1-chlorocyclopropyl p-tolyl sulfoxides possessing an N-aryl-substituted aminomethyl group were prepared from dichloromethyl p-tolyl sulfoxide, α,β-unsaturated carboxylic acid esters, and anilines in four steps. The deprotonation of the amine with t-BuMgCl followed by sulfoxide/magnesium exchange of the sulfoxides with i-PrMgCl led to the generation of the cyclopropylmagnesium carbenoids possessing a magnesium anilide moiety. Subsequent intramolecular nucleophilic substitution of the cyclopropylmagnesium carbenoids occurred in a 4-exo-tet manner to give the 2-azabicyclo[2.1.0]pentanes. The optically active 2-azabicyclo[2.1.0]pentane was synthesized using a p-tolylsulfinyl group as a chiral auxiliary. 相似文献
42.
ArS(ArSSAr)+ (arylbis(arylthio)sulfonium ions), which were generated and accumulated by the electrochemical oxidation of diaryl disulfides (ArSSAr) in CH2Cl2 at −78 °C, reacted with alkenes to give the corresponding diarylthio-substituted compounds in a stereospecific manner in good yields, when the reaction was quenched with a soft nucleophile, such as allylsilanes, ketene silyl acetals, and triethylamine. A mechanism involving the initial formation of an episulfonium ion followed by ring-opening by the attack of ArSSAr has been suggested. The reactions of ArS(ArSSAr)+ with alkynes also took place to give 1,2-diorganothio-substitued alkenes stereoselectively under similar conditions. 相似文献
43.
Formation of ketone acylals bearing trihaloacetoxy groups and their nucleophilic geminal disubstitution by fluoride ions were investigated. Cyclohexanone reacted with trifluoroacetic anhydride without catalyst to give gem-bistrifluoroacetates via a concerted bimolecular reaction. Treatment with hydrogen fluoride under mild conditions efficiently yielded the corresponding gem-difluorides. In this reaction process, trifluoroacetic acid was recovered and converted to trifluoroacetic anhydride using P2O5. Since gem-difluorides were derived from ketones, HF and P2O5, this constitutes a practical synthesis of gem-difluorides. 相似文献
44.
Takahiro Takayama Toshiki Mochizuki Kenichiro Todoroki Jun Zhe Min Hajime Mizuno Koichi Inoue Hiroyasu Akatsu Ichiro Noge Toshimasa Toyo'oka 《Analytica chimica acta》2015
Chiral metabolites are found in a wide variety of living organisms and some of them are understood to be physiologically active compounds and biomarkers. However, the overall analysis of chiral metabolomics is quite difficult due to the high number of metabolites, the significant diversity in their physicochemical properties, and concentration range from metabolite-to-metabolite. To solve this difficulty, we developed a novel approach for chiral metabolomics fingerprinting and chiral metabolomics extraction, which is based on the labeling of a pair of enantiomers of chiral derivatization reagents (i.e., DMT-(S,R)-Pro-OSu and DMT-3(S,R)-Apy) and precursor ion scan chromatography of the derivatives. The multivariate statistics is also required for this strategy. The proposed procedures were evaluated by the detection of a diagnostic marker (i.e., d-lactic acid) using the saliva of diabetic patients. This method was used for the determination of biomarker candidates of chiral amines and carboxyls in Alzheimer's disease (AD) brain homogenates. As the results, l-phenylalanine (L-Phe) and l-lactic acid (L-LA) were identified as the decreased and increased biomarker candidates in the AD brain, respectively. Therefore, the proposed approach seems to be helpful for the determination of non-target chiral metabolomics possessing amines and carboxyls. 相似文献
45.
Toshiki Mochizuki Takahiro TakayamaKenichiro Todoroki Koichi InoueJun Zhe Min Toshimasa Toyo’oka 《Analytica chimica acta》2015
A novel triazine-type chiral derivatization reagent, i.e., (S)-2,5-dioxopyrrolidin-1-yl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl) pyrrolidine-2-carboxylate (DMT-(S)-Pro-OSu), was developed for the highly sensitive and selective detection of chiral amines and amino acids by UPLC–MS/MS analysis. The enantiomers of amino acids were easily labeled with the reagents at room temperature within 40 min in an alkaline medium containing triethylamine. The diastereomers derived from proteolytic amino acids, except serine, were well separated under isocratic elution conditions by reversed-phase chromatography using an ODS column (Rs = 1.2–9.0). dl-Serine was separated by use of an ADME column which has relatively higher polar surface than the conventional ODS column. The characteristic product ions, i.e., m/z 195.3 and m/z 209.3, were detected from all the diastereomers by the collision-induced dissociation of the protonated molecule. A highly sensitive detection on the amol–fmol level was obtained from the selected reaction monitoring (SRM) chromatogram. The chiral amines (e.g., adrenaline and noradrenaline) labeled with DMT-(S)-Pro-OSu were also well separated and sensitively detected by the present procedure. The method using DMT-(S)-Pro-OSu was used for the determination of dl-amino acids in the human saliva from healthy volunteers. Various l-amino acids were identified in the saliva. Furthermore, d-alanine (d-Ala) and d-proline (d-Pro) were also detected in relatively high concentrations (>5%). The ratio was higher in male saliva than in female saliva. However, the difference in the ratio of d-Ala for one day was not very high and the effect of foods and beverage seemed to be negligible. Based on the results using l-Ala-d3, the d-Ala in saliva seemed to be produced due to the racemization with some enzymes such as racemase. The racemization reaction was reversible, i.e., d-Ala-d3 was also racemized to l-Ala-d3 in saliva. Thus, care should be taken during the analysis of dl-amino acids in saliva. The present method using DMT-(S)-Pro-OSu may be applicable for the determination of chiral amine metabolomics, because the resulting derivatives produce the same product ions without relation to the compounds and show highly sensitive detection in the SRM mode of MS/MS. Consequently, DMT-(S)-Pro-OSu seems to be a useful chiral derivatization reagent for the determination of amines and amino acids in biological samples. 相似文献
46.
Toshiki Kihara 《Experimental Mechanics》2004,44(5):455-460
The method of measurement of a three-dimensional photoelastic model with rotated principal axes has not yet been fully experimentally
established. It is known that a three-dimensional photoelastic model can be reduced to an optically equivalent model. In this
paper, the optically equivalent model is realized from a stratified model consisting of two layers of the frozen stress model.
The secondary principal stress direction and the relative phase retardation of the frozen disk model in the stratified frozen
stress model are determined for the entire field from Stokes parameters obtained by scattered-light photoelasticity using
unpolarized light. The accuracy of these values is confirmed by a comparison with results only from the frozen stress disk
model. 相似文献
47.
Toshiki Mochizuki Kenichiro TodorokiKoichi Inoue Jun Zhe MinToshimasa Toyo’oka 《Analytica chimica acta》2014
l-Pyroglutamic acid succinimidyl ester (l-PGA-OSu) and its isotopic variant (l-PGA[d5]-OSu) were newly synthesized and evaluated as the chiral labeling reagents for the enantioseparation of amino acids, in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. The enantiomers of amino acids were easily labeled with the reagents at 60 °C within 10 min in an alkaline medium containing triethylamine. Although all the diastereomers derived from 18 proteolytic amino acids could not be satisfactorily separated, the pairs of 9 amino acids were completely separated by reversed-phase chromatography using the small particle (1.7 μm) ODS column (Rs = 1.95–8.05). The characteristic daughter ions, i.e., m/z 84.04 and m/z 89.04, were detected from all the derivatives by the collision induced dissociation of the protonated molecular ions. A highly sensitive detection at a low-fmol level (0.5–3.2 fmol) was also obtained from the selected reaction monitoring (SRM) chromatograms. An isotope labeling strategy using light and heavy l-PGA-OSu for the differential analysis of the dl-amino acids in different sample groups is also presented in this paper. The differential analysis of biological sample (i.e., human serum) and food product (i.e., yogurt) were tried to demonstrate the efficiency of the proposed method. The ratios of the dl-amino acids in human serum samples, spiked with the different concentrations of d-amino acids, were determined by the procedures using l-PGA-OSu and l-PGA[d5]-OSu. The d/l ratios in the two sample groups at different concentrations of amino acids were similar to the theoretical values. Furthermore, the ratios of d/l-alanine values in different yogurt products were comparable to the ratios obtained from the d/l values using only light reagent (i.e., l-PGA-OSu). Consequently, the proposed strategy is useful for the differential analysis not only in biological samples but also in food products. 相似文献
48.
Generation of carbocations by the "cation pool" method followed by reaction with dimethyl sulfoxide (DMSO) gave the corresponding alkoxysulfonium ions. Alkoxysulfonium ions could also be generated by in situ DMSO trapping of electrochemically generated carbocations. The resulting alkoxysulfonium ions were transformed into carbonyl compounds by treatment with triethylamine. The present integrated electrochemical-chemical oxidation can be applied to the oxidation of diarylmethanes to diaryl ketones, toluenes to benzaldehydes, and aryl-substituted alkenes to 1,2-diketones. Moreover, the oxidation of unsaturated compounds bearing a nucleophilic group in an appropriate position gives cyclized carbonyl compounds. 相似文献
49.
tert-Butyl hypoiodite (t-BuOI) was found to be a powerful reagent for the cycloaddition of oximes and alkenes/alkynes, leading to the formation of a variety of isoxazolines or isoxazoles under mild conditions. 相似文献
50.
A Monte Carlo model has been developed to describe the formation of bimetallic nanoparticles via the microemulsion route. The motivation stems from the need to understand the kinetics of nanoparticle formation in microemulsion droplets in order to determine the best experimental conditions to synthesize a nanoparticle with a given structure. We focus our study on the influence of the homogeneous and heterogeneous critical nucleus sizes of both metals on nanoparticle structure, as well as the role played by the surfactant film flexibility. The study reveals that the final structure is sensitive to changes in the critical nucleus numbers, because these parameters determine the rate of nucleation. An increase in the difference between nucleation rates of both metals gives rise to a better segregation of metals in the final nanoparticle. Likewise, as long as the formation of heterogeneous seeds is faster, the degree of alloying is greater. Finally, a fast material intermicellar exchange leads to a better mixture of metals, so the influence of the critical nucleus sizes on nanoparticle structure becomes less pronounced as the flexibility of surfactant film is increased. 相似文献