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21.
Broja M. Mandal Joseph P. Kennedy Rodney Kiesel 《Journal of polymer science. Part A, Polymer chemistry》1978,16(4):821-831
An improved synthesis of trivinylaluminum (V3Al) is described. The proton magnetic resonance (PMR) spectrum of V3Al was recorded and analyzed. A new vinylation method involving the use of V3Al as the vinylating agent has been developed, and the vinylation of organic halides by V3Al was studied at ?30, ?50 and ?70°C. Primary alkyl chlorides, such as methyl and methylene chloride, do not react with V3Al and were used as solvents. Secondary chlorides such as 2-chloropropane also do not react. t-Butyl chloride gives rise to t-butylethylene (70–98%), depending on reaction conditions, and the allylic chlorides, 3-chloro-1-butene, and 3-chloro-3-methyl-1-butene, yield the expected vinylated products and their isomers (~90%). Allyl and benzyl chloride do not react under the conditions tried. The reaction between V3Al and the ditertiary dichloride 2,6-dichloro-2,6-dimethylheptane yields several isomeric C13H24 and C11H20 hydrocarbons; however, surprisingly, C9H16 does not form. The C13 hydrocarbons arise by divinylation at the termini of the dichloride, while the C11 hydrocarbons are formed by vinylation at one and proton elimination at the other terminus of the dichloride. The presence of unsaturated C13H24 and C11H20 isomers is most likely due to proton induced isomerization. These results are explained by a proximity effect involving vinylation at one end of the dichloride by V3Al followed by rapid reaction of the second chlorine (mostly) by V2AlCl generated in situ during the first vinylation in the proximity of the chloride. At the other chlorine terminus V2AlCl causes either a second vinylation (leading to C13 hydrocarbons) or a proton elimination (leading to C11 hydrocarbons). The absence of C9H16 among the reaction products indicates that V3Al exclusively effects vinylation. The RCl + V3Al ← RV + V2AlCl reaction may be regarded as a model for initiation followed by immediate termination in cationic olefin polymerization, a process leading to vinyl-ended polymers. 相似文献
22.
Diphenyl diselenides and disulfides undergo facile cleavages by indium(I) iodide and the corresponding generated selenate and thiolate anions condense in situ with alkyl or acyl halides present in the reaction mixture. Thus, a simple, efficient, and general procedure has been developed for the synthesis of unsymmetrical diorganyl selenides, sulfides (thioethers), selenoesters, and thioesters by this one-pot reaction at room temperature. 相似文献
23.
A Koll A Filarowski D Fitzmaurice E Waghorne A Mandal S Mukherjee 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(1):197-207
Two new orthohydroxy Schiff bases, 7-phenylsalicylidene benzylamine (PSBA) and 7-ethylsalicylideneaniline (ESA) have been synthesized. The excited state intramolecular proton transfer (ESIPT) and the structure of PSBA and ESA in its crystalline form and in the solvents n-hexane, n-heptane and 1,4-dioxane have been investigated by means of absorption, emission and nanosecond spectroscopy at room temperature and 77K. One ground state species has been detected both in neutral and basic solutions of both PSBA and ESA: the cis-enol form with an intramolecular hydrogen bond. The ESIPT and formation of keto tautomer are evidenced by a large Stokes shifted emission (approximately 12000 cm(-1)) at room temperature only in the case of ESA. On the other hand the keto tautomer is the predominant species at 77K in a solid matrix and as a solid sample at room temperature both in the case of ESA and PSBA. In the case of both ESA and PSBA the more intense, higher energy emission is due to the species which has not undergone ESIPT and attributed mainly due to cis-enol form. The trans-enol form is also observed by changing the excitation wavelength. Both the compounds are found to undergo a structural change to a zwitterionic and intermolecular hydrogen bonded form in the presence of a strong base like triethylamine. From the nanosecond measurements and quantum yield of fluorescence we have estimated the decay rates of proton transfer reaction in the case of PSBA. Our theoretical calculation at the AM1 level of approximation shows that the ground singlet state has a rather large activation barrier both in the case of PSBA and ESA. The barrier height is much lower on the corresponding excited singlet surface only in the case of ESA. The process is predicted to be endothermic in the ground state and exotherrmic in the excited singlet state. 相似文献
24.
A. Mandal A. Koll A. Filarowski D. Majumder S. Mukherjee 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1999,55(14):2861
A new orthohydroxy Schiff base, 7-ethylsalicylidenebenzylamine (ESBA) has been synthesised. The excited state intramolecular proton transfer (ESIPT) processes have been investigated by means of absorption, emission and nanosecond spectroscopy at room temperature and at 77 K in non polar solvents. The ESIPT is evidenced by a large Stokes shifted emission (11 000 cm−1) only at 77 K. From fluorescence and excitation spectra it is suggested that at least three different species are present in the excited state at room temperature. Our theoretical calculation at AM1 level confirm the cis-isomer to be the only viable form in the ground state. 相似文献
25.
K. Chabita P. C. Mandal S. N. Bhattacharyya 《Journal of Radioanalytical and Nuclear Chemistry》1994,188(2):133-148
Dilute aqueous solutions of cytosine were irradiated with60Co -rays under N2O saturated conditions at different pH and in the presence of Cu(II) ions at neutral pH. The base degradation decreased from neutral to acidic and basic conditions. In the presence of metal ions at neutral pH conditions there was a significant increase in the base degradation compared to that in the absence of metal ions under similar conditions. From the difference absorption spectra and fluorescence behavior of the irradiated solutions it was observed that the major radiolytic products of cytosine under different conditions are cytosine glycols, 5-hydroxycytosine, hydroxy-hydrocytosine and cytosine dimers. The yields of dimers is maximum in neutral conditions and it decreased from basic to acidic conditions. However, in the presence of Cu(II) ions formation of cytosine dimers is completely restricted and there is an increase in the yields of cytosine glycol, hydroxy-hydrocytosine and 5-hydroxycytosine. From the post-radiolytic changes in absorption and fluorescence behavior of irradiated solutions, it is revealed that some of the radiolytic products, namely cytosine glycol and hydroxy-hydrocytosine decompose to 5-hydroxycytosine and cytosine, respectively. 相似文献
26.
A series of compositions with the general formula RE2Hf2O7 (RE=Dy, Ho, Er, Tm, Y and Lu) was prepared by a standard solid-state route and characterized by powder X-ray diffraction (XRD) and Raman spectroscopy. As per theoretical modeling reported in literature, some of these materials were predicted to exist in pyrochlore lattice. However, a careful X-ray diffraction, Raman spectroscopic and synchrotron radiation-XRD study revealed that under the experimental conditions used in the present investigation, out of all the RE2Hf2O7 samples only Dy2Hf2O7 has got a tendency to form a pyrochlore structure. All the other (Ho, Er, Tm, Lu, Y) hafnates crystallize in a defect-fluorite structure. In order to further ascertain these inferences, a few more RE2Hf2O7 samples (La, Nd, Sm) i.e., with larger RE3+ ions were also prepared and the results were compared. 相似文献
27.
Bholanath Mandal 《International journal of quantum chemistry》2005,103(2):140-148
A graph theoretical procedure for obtaining eigenvalues of linear chains and cycles having alternant vertex weights (h1, h2, h1, h2, h1, h2, …) and the same edge weight (k) have been developed. The eigenvalues of some complicated graphs, such as graphs of linear polyacenes, methylene‐substituted linear polyacenes and cylindrical polyacene strips, stack graphs, and reciprocal graphs have been shown to be generated in closed analytical forms by this procedure. Many such graphs represent chemically important molecules or radicals. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
28.
Mukhopadhyay S Chatterjee PB Mandal D Mostafa G Caneschi A van Slageren J Weakley TJ Chaudhury M 《Inorganic chemistry》2004,43(11):3413-3420
Three coordination polymers of copper(II), viz. ([Cu(ida)(4,4'-bipyH)]ClO(4))( proportional, variant ) (1), ([Cu(2)(ida)(2)(micro-4,4'-bipy)].2H(2)O)( proportional, variant ) (2), and [Cu(2)(ida)(2)(bpa)]( proportional, variant ) (3) have been synthesized by the process of self-assembly using Cu(ida) [ida = iminodiacetate(2-)] as the building block and 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane (bpa) as linkers. Crystals of 1 are orthorhombic, of space group Pna2(1), with a = 13.8956(12) A, b = 16.3362(16) A, c = 7.3340(12), and Z = 4. Both compounds 2 and 3 crystallize in monoclinic space group P2(1)/a with a = 10.1887(8) A (9.6779(10) A for 3), b = 8.0008(11) A (9.1718(10) A), c = 11.6684(9) A (12.9144(12) A), beta = 98.307(11) degrees (102.796(18) degrees ), and Z = 2 (2). Compound 1 has a zigzag chain structure with an extensive hydrogen-bonded network while compounds 2 and 3 are honeycomb (6,3) nets with interpenetrating structures. Variable temperature (2-300 K) magnetic study indicates the presence of weak antiferromagnetic interactions (J = 0.82 +/- 0.01 cm(-)(1)) in 1 and ferromagnetic in 2 (J = -0.45 +/- 0.05 cm(-)(1)) and 3 (J = -0.21 +/- 0.02 cm(-)(1)). The extent of planarity of the bridging "Cu-O-C-O-Cu" moiety, acting as the super-exchange pathway between the neighboring copper centers, probably controls the sign of the magnetic exchange coupling in these compounds. 相似文献
29.
Sreemanta Mitra Amrita Mandal Anindya Datta Sourish Banerjee Dipankar Chakravorty 《Journal of magnetism and magnetic materials》2012
Nanosheets of nickel with thickness equal to 0.6 nm have been grown within the interlayer spaces of Na-4 mica. The sheets are made up of percolative clusters of nanodisks. Magnetization characteristics indicate a superparamagnetic behavior with a blocking temperature of 428 K. The magnetic anisotropy constant as extracted from the coercivity data has been found to be higher than that of bulk nickel by two orders of magnitude. This is ascribed to a large aspect ratio of the nickel nanophase. The Bloch exponent is also found to be considerably different from that of bulk nickel because of a size effect. The Bloch equation is still found to be valid for the two dimensional structures. 相似文献
30.
Varadhan Krishnakumar Kesarla Mohan Kumar Badal Kumar Mandal Fazlur-Rahman Nawaz Khan 《Research on Chemical Intermediates》2012,38(8):1881-1892
A simple and green protocol, developed utilizing an efficient, heterogeneous and recyclable catalyst, i.e. zinc oxide nanoparticles (ZnO NPs)-mediated synthesis of N-arylhomophthalimides and benzannelated isoquinolinones, is reported. The structures of the desired products were characterized by FTIR, 1H NMR, 13C NMR, and HRMS techniques. The ZnO NPs exhibited excellent catalytic activity and the proposed methodology is capable of providing the desired products in good yield and purity. 相似文献