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11.
Januszewski E Lorbach A Grewal R Bolte M Bats JW Lerner HW Wagner M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(45):12696-12705
The targeted hydrolysis of the 9,10-dihydro-9,10-diboraanthracene adduct (Me(2)S)HB(C(6)H(4))(2)BH(SMe(2)) (1) with 0.5 equiv of H(2)O leads to formation of the borinic acid anhydride [(Me(2)S)HB(C(6)H(4))(2)B](2)O (2) and thereby provides access to the field of unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracenes. Compound 2 reacts with tBuC≡CH to give the corresponding vinyl derivative in an essentially quantitative conversion. Subsequent cleavage of the B-O-B bridge by LiAlH(4) with formation of hydridoborate functionalities is possible but is accompanied by partial B-C(vinyl) bond degradation. This situation changes when the related mesityl derivative [MesB(C(6)H(4))(2)B](2)O (7) is employed, which can be synthesized from BrB(C(6)H(4))(2)BBr (6) by treatment with 1 equiv of MesMgBr and subsequent hydrolysis. The reaction of 7 with LiAlH(4) in tetrahydrofuran (THF) furnishes Li[MesB(C(6)H(4))(2)BH(2)] (8); hydride elimination with Me(3)SiCl leads to formation of the THF adduct MesB(C(6)H(4))(2)BH(THF) (9·THF). Alternatively, 7 can be transformed into the bromoborane MesB(C(6)H(4))(2)BBr (10) by treatment with BBr(3). A Br/H-exchange reaction between 10 and Et(3)SiH yields the donor-free borane MesB(C(6)H(4))(2)BH (9), which forms B-H-B bridged dimers (9)(2) in the solid state. The vinyl borane MesB(C(6)H(4))(2)BC(H)=C(H)Mes (14) is accessible from MesC≡CH and either 9·THF or 9. Compared with the related compound Mes(2)BC(H)=C(H)Mes, the electronic absorption and emission spectra of 14 reveal bathochromic shifts of Δλ(abs)=17 nm and Δλ(em)=74 nm, which can be attributed to the rigid, fully delocalized π framework of the [MesB(C(6)H(4))(2)B] chromophore. 相似文献
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The spectral characteristics of different drugs i.e. sulfanilamide, sulfanilic acid, sulfosalicylic acid dihydrate (SSAD) and sulfamethoxazole in aqueous α-cyclodextrin (CD) have been investigated at neutral pH. The formation of inclusion complexes of sulfa drugs with α-CD leads to the changes in fluorescence and absorption spectra which further enable the calculation of association constant of the bind processes by implementing the non-linear regression on the experimental data. The standard Gibbs energy ΔG was also calculated for the systems in which complex formation was observed. The α-CD study indicates that the sulpha drugs form 1:1 inclusion complex with α-CD. 相似文献
15.
Surbhi Grewal Pravesh Kumar Dr. Saonli Roy Dr. Indu Bala Dr. Chitranjan Sah Dr. Santanu Kumar Pal Dr. Sugumar Venkataramani 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(19):e202104602
Two tripodal C3-symmetric photoswitchable molecular systems T1 and T2 are reported that have extended conjugation at external and internal positions using an acryl group. The influence of the extended π-bonds in their absorption properties, thermal relaxation of the photoisomers and their propensities in forming supramolecular self-assemblies have been explored through spectroscopy, and microscopic studies. In particular, the investigations on the self-assembly have been carried out using scanning electron microscopy (SEM), transmission electron microscopy (TEM), polarized optical microscopy (POM), X-ray diffraction studies (XRD) and atomic force microscopy (AFM). Remarkably, the position of the acryl group influences the behaviour of the two target molecules in supramolecular assembly, and also in the formation of photoresponsive organic hydrogels or microcrystals. 相似文献
16.
Possible modes of deactivation of Jacobsen's Co-salen catalyst during the hydrolytic kinetic resolution (HKR) of epichlorohydrin were explored by UV-vis spectroscopy, X-ray absorption spectroscopy, and electrospray ionization mass spectrometry, combined with recycling studies. Although an active Co(III)-salen catalyst deactivated substantially after multiple cycles without regeneration, the catalyst maintained its +3 oxidation state throughout the runs. Thus, deactivation of Co-salen during HKR was not the result of Co reduction. The mass spectrum of a deactivated material showed that catalyst dimerization does not account for the loss of activity. Results from various catalyst pretreatment tests, as well as from catalysts containing various counterions (acetate, tosylate, chloride, iodide) indicated that the rate of addition of the Co-salen counterions to epoxide forming Co-OH during the reaction correlated with deactivation. The extent of counterion addition to epoxide was influenced by the exposure time and the nucleophilicity of the counterion. An oligo(cyclooctene)-supported Co-OAc salen catalyst, which was 25 times more active than the standard Co-salen catalyst, was recycled multiple times with negligible deactivation. 相似文献
17.
M. S. Alam A. A. S. Awwal P. McWhorter R. Venkatesh S. Mathur M. Dugar B. Grewal 《Optics & Laser Technology》2000,32(4)
A new synthetic discriminant-function-based amplitude modulated phase-only filtering technique is proposed for scale invariant pattern recognition. This technique has been found to yield improved correlation output when compared with the alternate techniques. The proposed technique is inherently suitable for optical implementation using the currently available spatial light modulators. Simulation results confirm the effectiveness of the proposed technique. 相似文献
18.
Sarvendra Kumar Surbhi M. K. Yadav 《Russian Journal of Physical Chemistry B, Focus on Physics》2018,12(3):383-393
The FTIR and FT-Raman spectra of tetrahydroxy-1,4quinone hydrate have been recorded in the regions 4000–400 and 3500–50 cm–1 respectively. Using the observed Fourier-transform infrared spectroscopy (FTIR) and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound has been carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by the density functional theory (DFT/B3LYP) and Hartree–Fock (HF) method with 6-311+G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamental vibrations is very small. A detailed interpretation of the infrared and Raman spectra of tetrahydroxy-1,4quinone hydrate is also reported. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. 相似文献
19.
Bhargava S Hou J Parvez M Sorensen TS 《Journal of the American Chemical Society》2005,127(11):3704-3705
The first X-ray crystal structures of two different bicyclo[1.1.0]butanones show a very long transannular bond of 1.69 A and a large carbonyl pyramidal distortion of 0.26 A out of the plane of the three carbons. These features are those expected of molecules with a hybrid cyclopropanone-oxyallyl structure, and these structures differ markedly from those of the parent bicyclo[1.1.0]butane skeleton. 相似文献
20.
Navjeet Kaur Yamini Verma Pooja Grewal Neha Ahlawat Pranshu Bhardwaj Nirmala Kumari Jangid 《合成通讯》2020,50(11):1567-1621
AbstractThe metal-assisted synthesis of heterocyclic compounds is known to be one of the extremely developing as well as significant concepts of organic chemistry. Because of their expensive, complex working of the instrument and difficult procedures, the methodologies used earlier for the heterocycle synthesis were less amicable to the researchers. The Pd(OAc)2-mediated cyclic reactions have been recognized to be very effective for both the stereoselective as well as regioselective formation of the 5-membered N-bearing heterocyclic compounds. The different uses of palladium acetate, as a catalyst in the formation of 5-membered N-containing polyheterocycles, are covered in this review article. 相似文献