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1.
Pure (7E,9Z-7, 9-dodecadien-1-yl acetate (1), the sex pheromone of Lobesiabotrana, has been prepared in 21.6% overall yield by a reaction scheme involving; (i) the cross-coupling of (E) - 8 - (2 - tetrahydropyranyloxy) -1 - octenyldisiamylborane with 1 - bromo - 1 - butyne, in the presence of a Pd (O) catalyst and base; (ii) the acetylation of the crude product of this reaction; (iii) the (Z)-stereoselective reduction of the obtained conjugated (E)-enyn-1-yl acetate. (E)-9,11-Dodecadien-1-yl acetate (2), a sex pheromone component of Diparopsiscastanea, has been analogously obtained (in 54.3% overall yield) by cross-coupling of (E) - 10 - (2 - tetrahydropyranyloxy) - 1 - decenyl borane with vinyl bromide, in the presence of a Pd (O) catalyst and base, followed by acetylation of the crude product. Compound 2, which was 87.7% chemically pure, was purified by column chromatography over SiO2-AgNO3. Chemically pure (9Z, 11E) - 9,11 - tetradecadien - 1 - yl acetate (3), a sex pheromone component of Spodopteralittoralis, has been prepared (in 30.2% overall yield) by reaction of 10 - (2 - tetrahydropyranyloxy) - 1 - decynylamagnesium bromide with (E)-1-iodo-1-butene, in the presence of a Pd (O) catalyst, followed by acetylation of the crude product and by (Z)-stereoselective reduction of the obtained (E)-enyn-1-yl acetate.The stereoisomeric purity of 1, 2 and 3 has been evaluated by glc analysis on glass capillary columns or by reverse phase hplc analysis. 相似文献
2.
(S)-β-Bisabolene, (S)-1, was synthetized by a synthetic route in which (S)-4-methyl-3-cyclohexene carboxylic acid, (S)-10, which was the key intermediate, was prepared via a highly diastereoselective TiCl4-catalyzed Diels-Alder reaction between isoprene and the acrylate of commercial (R)-pantolactone, followed by hydrolysis. Compound (S)-10 was then converted into ketone (S)-13 using two different procedures. The best one of these, as regards the degree of stereospecificity, involved the reaction of (S)-10 with 2 equiv of 4-methyl-3-penten-1-yllithium, 14, in the presence of CeCl3, and gave (S)-13 having ca. 84% ee. The Zr-promoted methylenation of this ketone afforded highly enantiomerically enriched (S)-1. 相似文献
3.
Amanda S. Santana Diego B. Carvalho Nadla S. Cassemiro Luiz H. Viana Gabriela R. Hurtado Marcos S. Amaral Najla M. Kassab Palimécio G. Guerrero Jr. Sandro L. Barbosa Miguel J. Dabdoub Adriano C.M. Baroni 《Tetrahedron letters》2014
A simple synthesis of 3-iodothiophenes was demonstrated using a wide range of (Z)-thioenynes. The key step in the iodocyclofunctionalization was the selective reduction of the triple bond in (Z)-thioenynes by the addition of iodine as an electrophilic agent. The 3-iodothiophenes were obtained in good to excellent yields of 61–92%. The 3-iodothiophenes were used as substrates in Sonogashira cross-coupling reactions to obtain thiophene acetylenes. 相似文献
4.
Adriano Costa de Camargo Hernn Speisky Raquel Bridi Paula Núez Pizarro Arturo Larena Ana Clara da C. Pinaffi-Langley Fereidoon Shahidi Andrs R. Schwember 《Molecules (Basel, Switzerland)》2022,27(3)
The Valparaiso region in Chile was decreed a zone affected by catastrophe in 2019 as a consequence of one of the driest seasons of the last 50 years. In this study, three varieties (‘Alfa-INIA’, ‘California-INIA’, and one landrace, ‘Local Navidad’) of kabuli-type chickpea seeds produced in 2018 (control) and 2019 (climate-related catastrophe, hereafter named water stress) were evaluated for their grain yield. Furthermore, the flavonoid profile of both free and esterified phenolic extracts was determined using liquid chromatography-mass spectrometry, and the concentration of the main flavonoid, biochanin A, was determined using liquid chromatography with diode array detection. The grain yield was decreased by up to 25 times in 2019. The concentration of biochanin A was up to 3.2 times higher in samples from the second season (water stress). This study demonstrates that water stress induces biosynthesis of biochanin A. However, positive changes in the biochanin A concentration are overshadowed by negative changes in the grain yield. Therefore, water stress, which may be worsened by climate change in the upcoming years, may jeopardize both the production of chickpeas and the supply of biochanin A, a bioactive compound that can be used to produce dietary supplements and/or nutraceuticals. 相似文献
5.
We obtain pulse-driven Rabi oscillations guided by a generalization of the rotating-wave approximation to include, in the optical-Bloch equations, two-level systems with a time-varying transition energy. We achieve this by using chirped pulses with the central frequency given by the time-varying transition energy. Using this approach, we predict Rabi oscillations in intersubband transitions in a two-subband n-type modulation-doped quantum well by taking into account the time-dependent intersubband energy-gap renormalization due to depolarization-shift effects. We obtain Rabi oscillations for jpi (j=0,1,2, ) pulses in the presence of dephasing. 相似文献
6.
Here, we demonstrate that platelet graphite nanofibers (PGNFs) exhibit fast heterogeneous electron‐transfer rates for a wide variety of compounds such as FeCl3, ferrocyanide, dopamine, uric acid, ascorbic acid, and the reduced form of β‐nicotinamide adenine dinucleotide. The electrochemical properties of PGNFs are superior to those of multiwalled carbon nanotubes (MWCNTs) or graphite microparticles (GMPs). Transmission electron microscopy and Raman spectroscopy reveal that this arises from the unique graphene sheet orientation of such platelet nanofibers, which accounts for their unparalleled high ratio of graphene edge planes versus basal planes. 相似文献
7.
Haraguchi SK Silva AA Vidotti GJ dos Santos PV Garcia FP Pedroso RB Nakamura CV de Oliveira CM da Silva CC 《Molecules (Basel, Switzerland)》2011,16(2):1166-1180
A series of new thiosemicarbazones derived from natural diterpene kaurenoic acid were synthesized and tested against the epimastigote forms of Trypanosoma cruzi to evaluate their antitrypanosomal potential. Seven of the synthesized thiosemicarbazones were more active than kaurenoic acid with IC?? values between 2-24.0 mM. The o-nitro-benzaldehyde-thiosemicarbazone derivative was the most active compound with IC?? of 2.0 mM. The results show that the structural modifications accomplished enhanced the antitrypanosomal activity of these compounds. Besides, the thiocyanate, thiosemicarbazide and the p- methyl, p-methoxy, p-dimethylamine, m-nitro and o-chlorobenzaldehyde-thiosemicarbazone derivatives displayed lower toxicity for LLMCK? cells than kaurenoic acid, exhibing an IC?? of 59.5 mM. 相似文献
8.
Laíse Oliveira Resende Ana Cristina Honorato de Castro Adriano O. Andrade João Marcos Madurro Ana Graci Brito-Madurro 《Journal of Solid State Electrochemistry》2018,22(5):1365-1372
Epidemiological studies have demonstrated an association between the risk of cardiovascular events and increasing C-reactive protein (CRP) concentration. This paper reports the development of an immunosensor for the assessment of the cardiovascular process using anti-C-reactive protein antibody immobilized onto a gold-printed screen electrode. Positive and negative human sera were successfully evaluated using electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV), and atomic force microscopy (AFM). EIS results show that, after the incubation with positive serum for myocardial infarction, the resistance increased about two times in relation to the negative serum. A linear range from 6.25 to 50 μg mL?1 and detection limit of 0.78 μg mL?1 using DPV were obtained. The immunosensor developed for the CRP detection using gold electrode revealed efficacy and a potential use for the diagnosis and monitoring of the progression of cardiovascular diseases. 相似文献
9.
10.
Humeres E Debacher NA Franco JD Lee BS Martendal A 《The Journal of organic chemistry》2002,67(11):3662-3667
The acid decomposition of some p-substituted aryldithiocarbamates (arylDTCs) was observed in 20% aqueous ethanol at 25 degrees C, mu = 1.0 (KCl, for pH > 0). The pH-rate profiles showed a dumbell shape with a plateau where the observed first-order rate constant k(obs) was equal to k(o), the rate constant of the decomposition of the dithiocarbamic acid species. The acid dissociation constants of the dithiocarbamic acids (pK(a)) and their conjugate acids (pK(+)) were calculated from the pH-rate profiles. Comparatively, k(o) was more than 10(4)-fold faster than alkyldithiocarbamates (alkDTCs) with similar pK(N) (the acid dissociation constant of the parent amine). It was observed that the values of pK(a) and pK(+)were 5 and 8 units of pK, respectively, higher than the expected values from the pK(N) of alkylDTCs. The higher values were attributed to the inhibition of the delocalization of the nitrogen electron pair into the benzene ring because of the strong electron withdrawal effect of the thiocarbonyl group. Comparison of the activation parameters showed that the rate acceleration was due to a decrease in the enthalpy of activation. Proton inventory indicated the existence of a multiproton transition state, and it was consistent with an S to N proton transfer through a water molecule. There are two hydrogens contributing to a secondary SIE, and there are also two protons that are being transferred at the transition state to form a zwitterion followed by fast C-N bond cleavage. The mechanism could also be a concerted asynchronic process where the N-protonation is more advanced than the C-N bond breakdown. The kinetic barrier is similar to the torsional barrier of thioamides, suggesting that the driving force to reach the transition state is the needed torsion of the C-N bond that inhibits the resonance with the thiocarbonyl group and the aromatic moiety, increasing the basicity of the nitrogen and making the proton transfer thermodynamically favorable. 相似文献