scholarly journals Reaktive E=C(p – p)π-Systeme, XX [1] / Reactive E=C(p–p)π-Systems, XX [1]

1990 ◽  
Vol 45 (2) ◽  
pp. 148-160 ◽  
Author(s):  
Joseph Grobe ◽  
Marianne Hegemann ◽  
Duc Le Van

The vapour phase pyrolysis of the stannylphosphane Me3SnP(CF3)C2F5 (5) at 330 °C leads to 1,2-elimination of Me3SnF yielding a mixture of the two isomeric perfluorophosphaalkenes F3CP=C(F)CF3 (3) and F5C2P=CF2 (4) in a 3:1 molar ratio. 3 is more labile than 4 and proves to be similar to the perfluoro-3-phosphapent-2-ene F5C2P=C(F)CF3 (2) with respect to NMR data and chemical properties. On the other hand 4 resembles the perfluoro-2-phosphapropene F3CP=CF2 (1). These results have been deduced from the following reactivity studies: (i) The rate of dimerization being higher for 3 than for 4. (ii) Reaction of the mixture with diethylamine yielding the aminophosphane derivative F3CP(NEt2)CF(H)CF3 (13) as a product of 3 and the C-aminophosphaalkene F5C2P=C(F)NEt2 (14) as the derivative of 4. (iii) Reaction of the mixture with methanol giving the methoxyphosphane F3CP(OMe)CF(H)CF3 (15) from 3 and the secondary phosphane F5C2P(H)CF2OMe (16) from 4 as precursors. 3 and 4 prove to be effective dienophiles in reactions with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene, respectively, producing the corresponding Diels-Alder adducts 9 to 12. For these preparations 5 can be used as an equivalent of 3 in a one-pot procedure at 70 °C. On the other hand the phosphane HP(CF3)C2F5 (8) is suited as precursor for 3 in preparing HX addition products.

Agronomy ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 599 ◽  
Author(s):  
Nik Nurnaeimah ◽  
Nashriyah Mat ◽  
Khamsah Suryati Mohd ◽  
Noor Afiza Badaluddin ◽  
Nornasuha Yusoff ◽  
...  

Hydrogen peroxide (H2O2) is defined as a reactive oxygen species (ROS), able to cause damage to a variety of cellular structures. On the other hand, recent work has demonstrated that H2O2 can also act as a potent signaling molecule that mediates various physiological and biochemical processes in plants. This study was carried out to investigate the effects of H2O2 on the growth, mineral nutrient accumulation, as well as the biologic and chemical properties of Ficus deltoidea var. deltoidea. F. deltoidea plants were spray-treated with 0- (control), 8-, 16-, 30- and 60-mM H2O2 under field conditions. Plant height, leaf area, chlorophyll content, net photosynthetic rate, stomatal conductance and quantum yield of the F. deltoidea plants significantly increased after treatment with 16 and 30-mM H2O2. The results indicate that 60-mM H2O2 increased the accumulation of arsenic, iron and sodium content in the leaves of F. deltoidea. On the other hand, 8-mM H2O2 significantly enhanced the accumulation of arsenic, iron, calcium and potassium content in the syconium of F. deltoidea plants. In addition, H2O2 treatment did not produce any significant effects on antimony and magnesium accumulation in the leaves or the syconium of F. deltoidea plants. The results show that the F. deltoidea plant has strong antidiabetic properties and its α-glucosidase activity increased in treated plants compared to standard acarbose. Hydrogen peroxide, particularly in concentrations of 16 and 30 mM, increased the antioxidant activity, total phenolic and flavonoid content and the vitexin and isovitexin content. There was a positive correlation between antioxidant activity with total phenol and total flavonoid content in H2O2-treated plants. The quantitative analysis by HPTLC indicates that the amount of vitexin and isovitexin increased with the higher concentrations of H2O2. From this study, it can be concluded that spraying 16 and 30-mM H2O2 once a week enhances growth, mineral accumulation and stimulates bioactive compounds of the F. deltoidea plants.


1990 ◽  
Vol 68 (12) ◽  
pp. 2137-2143 ◽  
Author(s):  
Yao-Chang Xu ◽  
Michel Cantin ◽  
Pierre Deslongchamps

The syntheses of the acyclic dienynes 14a (cis-trans-acetylene) and 14b (trans-trans-acetylene) are described. The tandem macrocyclization and transannular Diels–Alder reaction of the allylic chloride 14b was conducted in the presence of Cs2CO3 at 85 °C in one-pot to provide tricyclic product 16, with the two hydrogens in ring B being cis. On the other hand, treatment of the allylic chloride 14a under the same conditions afforded 14-membered macrocycle 17, which could be transformed at 250 °C into a similar tricyclic product 18 with the two hydrogens in ring B being trans, along with an interesting by-product 19. The mechanism for the formation of 19 is also discussed. Keywords: stereocontrolled synthesis, macrocycle, tricyclic compound, transannular Diels–Alder reaction.


2019 ◽  
Author(s):  
Jingjia Huang ◽  
Gang Hu ◽  
Shaoyu An ◽  
Dongding Chen ◽  
Minglei Li ◽  
...  
Keyword(s):  
One Pot ◽  

N-alkylated 4-pyridones were obtained through a one-pot procedure involving either normal or interrupted Pummerer reactions between triflic anhydride activated sulfoxides and 4-fluoropyridine derivatives, followed by hydrolysis. On the other hand, triflic anhydride activated benzyl 6-fluoro-2-pyridyl sulfoxide could react with alkenes or alkynes to afford thiazolo[3,2-a]pyridin-5-ones, via the pyridinium salt intermediates.


2010 ◽  
Vol 10 (1) ◽  
pp. 1-6 ◽  
Author(s):  
R. Murillo ◽  
J. Sarasa ◽  
M. Lanao ◽  
J. L. Ovelleiro

The degradation of chlorpyriphos by different advanced oxidation processes such as photo-Fenton, TiO2, TiO2/H2O2, O3 and O3/H2O2 was investigated. The photo-Fenton and TiO2 processes were optimized using a solar chamber as light source. The optimum dosages of the photo-Fenton treatment were: [H2O2]=0.01 M; [Fe3 + ]=10 mg l−1; initial pH = 3.5. With these optimum conditions total degradation was observed after 15 minutes of reaction time. The application of sunlight was also efficient as total degradation was achieved after 60 minutes. The optimum dosage using only TiO2 as catalyst was 1,000 mg l−1, obtaining the maximum degradation at 20 minutes of reaction time. On the other hand, the addition of 0.02 M of H2O2 to a lower dosage of TiO2 (10 mg l−1) provides the same degradation. The ozonation treatment achieved complete degradation at 30 minutes of reaction time. On the other hand, it was observed that the degradation was faster by adding H2O2 (H2O2/O3 molar ratio = 0.5). In this case, total degradation was observed after 20 minutes.


2004 ◽  
Vol 1 (1) ◽  
pp. 110-115
Author(s):  
Baghdad Science Journal

We found that 4,5- diphenyl- 3(2- propynyl) thio- 1??-triazole [1? forms a complex with Pd (11) ion of ratio 1:1 which absorbs light in CH2CI2 at 400 nm, and 4,5- diphenyl- 3(2- propenyl) thio- 1,2,4- triazole [II] forms complexes with Pd (II) ion of ratio 1:1 which absorbs light at 390 nm, and of ratio 2:1 which absorbs light at 435 nm. On the other hand, we found that the new derivative 4- phenyl- 5( p- amino phenyl) -3- mercapto- 1,2,4- triazole ?111? forms complexes with Cu (II) ion of the ratio 1:1 which absorbs light at 380 nm, with Ni (II) ion of the ratio 3:1 which absorbs light at 358 nm; and with Co (11) ion of the ratio 3.2:1 which absorbs light at 588 nm. The ratio of the complexes were determined by measuring the electronic spectra of the complexes in CH2G2 and (CH^NCHO at different concentrations ofthe ligands and f?xed ' •' of the metal ion in every case, then applying the molar ratio plots on the data. Our results were confirmed by precipitating most ofthe above complexes in solid state, and then each complex was analyzed elementally.


2019 ◽  
Vol 9 (1) ◽  
Author(s):  
Shijiao Zhao ◽  
Jingtao Ma ◽  
Rui Xu ◽  
Xuping Lin ◽  
Xing Cheng ◽  
...  

AbstractZirconium compounds has been widely attention over the last decades due to its excellent physical and chemical properties. Zirconium nitride nanopowders were synthesized via a simple direct carbothermic nitridation process of internal gel derived zirconia in the presence of nano-sized carbon black. The effects of reaction temperature, dwell time and molar ratio of carbon black to Zr (C/Zr) on the phase composition, grain size and crystal parameters of products were studied. Based upon the analysis of crystallite phase evolution and microstructure characterization, it was found that zirconium oxynitride is intermediate product and then O atoms in oxynitride were extracted by oxygen getter, carbon black. Anion sites were directly replaced by N atoms to form rock-salt type nitride in carbothermic nitridation process.


2014 ◽  
Vol 631 ◽  
pp. 137-142 ◽  
Author(s):  
F.N. Oktar ◽  
H. Gokce ◽  
O. Gunduz ◽  
Y.M. Sahin ◽  
D. Agaogullari ◽  
...  

In this study the structural and chemical properties of barnacle shell based bioceramic materials (i.e. hydroxyapatite, whitlockite, monetite and other phases) were produced by using mechano-chemical (hot-plate) conversion method. Cleaned barnacle shells were ball milled down to <75µm in diameter. Differential thermal and gravimetric analyses (DTA/TGA) were performed to determine the exact CaCO3 content. Sample batches of 2g were prepared from the fine powders produced. For each batch, the required volume of an aqueous H3PO4 solution was calculated in order to set the stoichiometric molar ratio of Ca/P equal to 1.5 for ß-tricalcium phosphate (ß-TCP) or to 1.667 for hydroxyapatite (HA). The temperature was set to 80°C for 15 minutes to complete the process. After the titration of the equivalent amount of H3PO4 into the prepared solution, agitation was carried out on a hot-plate (i.e. mechano-chemical processing) for 8 hours. The sediments formed were dried and the resulting TCP and HA powders were calcined at 400°C and 800°C respectively. For complete characterization of the bioceramics produced, scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD) analyses were carried out. The current study proposes a simple, economic and time efficient method for nano-bioceramic production.


The above substance was discovered by M. Julien, of Abo, in Finland, amongst the products arising out of the distillation of calcined sulphate of iron, with crude nitre in iron retorts. It forms white acicular crystals by sublimation, and when passed through a green glass tube containing red-hot rock crystal, it is decomposed with the deposition of charcoal and evolution of chlorine. It is not altered by repeated sublimations in chlorine. It was analysed by passing its vapour over red-hot oxide of copper, by which chloride of copper and carbonic acid gas were produced: the former was de­composed by nitrate of silver, and the proportion of chlorine esti­mated by that of chloride of silver formed. From this and other experiments, the authors conclude that this substance consists of one portion of chlorine and two of carbon: they failed in their endea­vours to convert it into either of the other chlorides of carbon, to which, in its physical and chemical properties, it bears however a considerable resemblance.


Molecules ◽  
2021 ◽  
Vol 26 (24) ◽  
pp. 7485
Author(s):  
Kyung-Hyun Cho

α-synuclein (α-syn) is a major culprit of Parkinson’s disease (PD), although lipoprotein metabolism is very important in the pathogenesis of PD. α-syn was expressed and purified using the pET30a expression vector from an E. coli expression system to elucidate the physiological effects of α-syn on lipoprotein metabolism. The human α-syn protein (140 amino acids) with His-tag (8 amino acids) was expressed and purified to at least 95% purity. Isoelectric focusing gel electrophoresis showed that the isoelectric point (pI) of α-syn and apoA-I were pI = 4.5 and pI = 6.4, respectively. The lipid-free α-syn showed almost no phospholipid-binding ability, while apoA-I showed rapid binding ability with a half-time (T1/2) = 8 ± 0.7 min. The α-syn and apoA-I could be incorporated into the reconstituted HDL (rHDL, molar ratio 95:5:1:1, palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC):cholesterol:apoA-I:α-syn with the production of larger particles (92 Å) than apoA-I-rHDL (86 and 78 Å) and α-syn-rHDL (65 Å). An rHDL containing both apoA-I and α-syn showed lower α-helicity around 45% with a red shift of the Trp wavelength maximum fluorescence (WMF) from 339 nm, while apoA-I-HDL showed 76% α-helicity and 337 nm of WMF. The denaturation by urea addition showed that the incorporation of α-syn in rHDL caused a larger increase in the WMF than apoA-I-rHDL, suggesting that the destabilization of the secondary structure of apoA-I by the addition of α-syn. On the other hand, the addition of α-syn induced two-times higher resistance to rHDL glycation at apoA-I:α-syn molar ratios of 1:1 and 1:2. Interestingly, low α-syn in rHDL concentrations, molar ratio of 1:0.5 (apoA-I:α-syn), did not prevent glycation with more multimerization of apoA-I. In the lipid-free and lipid-bound state, α-syn showed more potent antioxidant activity than apoA-I against cupric ion-mediated LDL oxidation. On the other hand, microinjection of α-syn (final 2 μM) resulted in 10% less survival of zebrafish embryos than apoA-I. A subcutaneous injection of α-syn (final 34 μM) resulted in less tail fin regeneration than apoA-I. Interestingly, incorporation of α-syn at a low molar ratio (apoA-I:α-syn, 1:0.5) in rHDL resulted destabilization of the secondary structure and impairment of apoA-I functionality via more oxidation and glycation. However, at a higher molar ratio of α-syn in rHDL (apoA-I:α-syn = 1:1 or 1:2) exhibited potent antioxidant and anti-glycation activity without aggregation. In conclusion, there might be a critical concentration of α-syn and apoA-I in HDL-like complex to prevent the aggregation of apoA-I via structural and functional enhancement.


1993 ◽  
Vol 58 (6) ◽  
pp. 1445-1451 ◽  
Author(s):  
Lubomír Lochmann ◽  
Hana Jakubův ◽  
Lambert Brandsma

The presence or absence of lithium tert-pentoxide (t-PeOLi) in Superbases, prepared from butyllithium (BuLi) and potasium tert-pentoxide (t-PeOK), affects the metallation rate of toluene only slightly, the rate factors being between 1.0 and 0.3. Thus, lithium alkoxide is not essential for the high reactivity of Superbases. However, the ring-to-side chain metallation ratio is increased in the presence of t-PeOLi. On the other hand, an excess of t-PeOK (molar ratio t-PeOK/BuLi ≥ 3)considerably increases in the rate and yield of the side chain methallation of toluene and suppresses its ring mrtallation. In this way, alkoxides enable some control on regioselectivity in Superbase reactions.


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